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Adele MUCCI

Professore Associato
Dipartimento di Scienze Chimiche e Geologiche - Sede Dipartimento di Scienze Chimiche e Geologiche

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Pubblicazioni

2023 - Graphite-epoxy composites for bipolar plates: The gas permeability issue [Articolo su rivista]
Roncaglia, Fabrizio; Mucci, Adele; Romagnoli, Marcello; Spinelli, Luca; DI BONA, Alessandro; Biagi, Roberto
abstract

To sustain Hydrogen Economy, proton exchange membrane (PEM) devices are expected to play a central role in both the generation of clean hydrogen and its efficient employment. Bipolar plates are an essential part of PEM devices, therefore investigations directed to technical improvement and cost reduction of these components deserve considerable attention. This work represents an extension of our previous study on graphite-epoxy composites suitable for manufacturing bipolar plates and based on the use of cheap and commercially available materials. Through appropriate changes in the formulation of the composites and in the processing conditions, we succeeded in obtaining materials with full technical compliance, in terms of electrical conductivity and gas permeability. The processability and productivity of the method were improved as well, through the reduction of molding times. The variation of the properties of the samples with the molding pressure was analyzed.

2023 - Influence of chirality on the aggregation of a new A-π-D-π-A small molecule with a benzodithiophene core: Spectroscopic and morphological investigations [Articolo su rivista]
Parenti, Francesca; Capelli, Raffaella; Mucci, Adele; Mortalò, Cecilia; Paolicelli, Guido; Pigani, Laura; Vanossi, Davide; Caselli, Monica
abstract

2023 - La risonanza magnetica nella scienza degli alimenti. Con e-book [Monografia/Trattato scientifico]
Mannina, L.; Sobolev, A. P.; Proietti, N.; Di Tullio, V.; Angilè, F.; Bellomaria, A.; Bertelli, D.; Bertocchi, F.; Caligiani, L. R.; Mucci, A.; Righi, V.; Tenori, . L.; Urbinati, E.
abstract

2023 - Metabolic Profile of Whole Unstimulated Saliva in Patients with Sjögren's Syndrome [Articolo su rivista]
Setti, Giacomo; Righi, Valeria; Mucci, Adele; Panari, Lucia; Bernardelli, Giuditta; Tarentini, Elisabetta; Gambini, Anna; Consolo, Ugo; Generali, Luigi; Magnoni, Cristina; Meleti, Marco; Sandri, Gilda; Bellini, Pierantonio
abstract

: Primary Sjögren's Syndrome (pSS) is a multi-system autoimmune disease that involves the exocrine glands. Lymphocytes infiltrate the gland tissue, leading to anatomical modification and hypofunction. Even if the prognosis of pSS is favorable, quality of life is typically reduced due to the diverse manifestations of the disease. The aim of this study is to compare the salivary metabolomes of pSS with healthy controls (HCs). Seven cases were selected from a cohort of pSS patients, and six age- and sex-matched HCs were recruited from a cohort of volunteers. Whole unstimulated saliva was collected for NMR analysis. Our metabolomic analysis focused on 360 ms total echo 1D 1H NMR CPMG spectra. Metabolites detected with CPMG NMR spectra were assigned through 2D NMR spectra (COSY, TOCSY, and HSQC). About 50 metabolites were detected and assigned. Unsupervised exploratory PCA returned partial clustering, and PLS-DA improved the separation between pSS and HCs, highlighting a pool of metabolites distinctly describing each group. Despite the limited number of samples, the presented preliminary data are promising. PLS-DA indicated well-defined group separation, suggesting that the application of 1H-NMR metabolomics is suitable for the study of pSS.

2023 - NMR Metabolomics Based Study on Oral Malignant Disorders [Abstract in Atti di Convegno]
Gambini, A.; Setti, G.; Magnoni, C.; Meleti, M.; Mucci, A.; Righi, V.
abstract

2023 - STUDY OF THE EFFECTS OF SHORT-CHAIN PFASs ON HUMAN CELLS WITH NMR-METABOLOMICS [Abstract in Atti di Convegno]
Gambini, Anna; Mucci, Adele; Righi, Valeria
abstract

Application of NMR-based Metabolomics to study the effects of shortchain PFASs on an in vitro model

2022 - Graphite/epoxy composite for building Bipolar Plates [Articolo su rivista]
Spinelli, Luca; Roncaglia, Fabrizio; Biagi, Roberto; di Bona, Alessandro; Romagnoli, Marcello; Mucci, Adele
abstract

2022 - INVESTIGATING PHYSICAL PROPERTIES OF BIOPOLYMERS IN HAIR [Poster]
Righi, Valeria; Koufi, FOTEINI D.; Mucci, Adele
abstract

Hair is of outmost importance for the human body. Hair is composed of 1–8% external hydrophobic lipid epidermis, 80–90% α-helix or β-sheet conformation of parallel polypeptide chains to form water-insoluble keratin, less than 3% melanin pigment, and 0.6–1.0% trace elements, 10–15% moisture (Figure 1) [1]. Keratin proteins are insoluble in water and play a protective role. They possess a heterogeneous morphology that classifies them to the fibrous structural proteins. We received samples of hair that had undergone treatment with a hair mask prepared by a cosmetic company (Figure 2). The samples were taken in different timelines (table 1) to assess not only the reconstruction of keratin induced by the cosmetic formulation but also the possibility of a long-term effect on the hair

2022 - INVESTIGATING PHYSICAL PROPERTIES OF BIOPOLYMERS IN HAIR [Abstract in Atti di Convegno]
Righi, V.; Koufi, F. D.; Mucci, A.
abstract

Hair is of outmost importance for the human body. Hair is composed of 1–8% external hydrophobic lipid epidermis, 80–90% α-helix or β-sheet conformation of parallel polypeptide chains to form water-insoluble keratin, less than 3% melanin pigment, and 0.6–1.0% trace elements, 10–15% moisture [1]. Keratin proteins are insoluble in water and play a protective role. They possess a heterogeneous morphology that classifies them to the fibrous structural proteins. We received samples of hair that had undergone treatment with a hair mask prepared by a cosmetic company. The samples were taken in different timelines to assess not only the reconstruction of keratin induced by the cosmetic formulation but also the possibility of a long-term effect on the hair. Our main goal was the qualitative and quantitative assessment of the reconstructive effect on keratin. For the qualitative analysis, we employed the SEM-FEG technique and obtained a complete visualization of the keratin integrity. Moreover, liquid NMR was used to analyze the lipids extracted from the hair samples in a chloroform: methanol solution.

2022 - L’insegnamento dell’NMR in chimica organica e farmacia [Altro]
Mucci, A.
abstract

2022 - NEW SECONDARY METABOLITES IN THE AMPHINOMID FIREWORM HERMODICE CARUNCULATA [Poster]
Mucci, A.; Forti, L.; Simonini, R.; Ferrari, V.; Prevedelli, D.; Righi, S.
abstract

Eight betaine-derived novel compounds were found in extracts of the Mediterranean stinging fireworm Hermodice carunculata. The identification of their structures relies on 1D and 2D NMR (Fig. 1-3) and HPLC-ESI/HRMS spectra. Two types of terminal ammonium portions A and B and a series of different alkyl chains were identified (Fig. 4a,b). Their matching provides the structures of uncharacterized secondary metabolites, named carunculines, and their related isomers. These molecules differ from already known trimethylammonium inflammatory compounds (i.e. complanines) isolated from another amphinomid species, for the structures of the terminal ammonium groups (Fig. 4c) [1]. Carunculine anatomical distribution within H. carunculata was assessed by screening through HPLC-ESI/HRMS (Fig. 5, Table 1): their occurrence was revealed in all the body parts analyzed, both involved in predator-prey interactions [2], and mainly in the digestive apparatus. The results achieved reveal an array of different novel compounds from a chemically unknown species, improving knowledge on Marine Animal Products with chemical and biological potential for bioprospection [3]. Overall, these data reinforce the necessity of studying poorly-investigated taxa to expand knowledge on animal venom biology, their mechanisms of action and exploitation as promising source of drug molecules

2022 - NEW SECONDARY METABOLITES IN THE AMPHINOMID FIREWORM HERMODICE CARUNCULATA [Abstract in Atti di Convegno]
Mucci, A.; Forti, L.; Simonini, R.; Ferrari, V.; Prevedelli, D.; Righi, S.
abstract

Eight betaine-derived novel compounds were found in extracts of the Mediterranean stinging fireworm Hermodice carunculata. The identification of their structures relies on 1D and 2D NMR and HPLC-ESI/HRMS spectra (Fig. 1). Two types of terminal amine portions and a series of different alkyl chains were identified. Their matching provides the structures of uncharacterized secondary metabolites, named “carunculines”, and their related isomers. These molecules differ from already known trimethylammonium inflammatory compounds (i.e. “complanines”) isolated from another amphinomid species, for the structures of the terminal ammonium groups [1]. Carunculine anatomical distribution within H. carunculata was assessed by screening through HPLC-ESI/HRMS: their occurrence was revealed in all the body parts analyzed, both involved in predator-prey interactions [2], and mainly in the digestive apparatus. The results achieved reveal an array of different novel compounds from a chemically unknown species, improving knowledge on Marine Animal Products with chemical and biological potential for bioprospection. Overall, these data reinforce the necessity of studying poorly-investigated taxa to expand knowledge on animal venom biology, their mechanisms of action and exploitation as promising source of drug molecules.

2022 - Novel Natural Compounds and Their Anatomical Distribution in the Stinging Fireworm Hermodice carunculata (Annelida) [Articolo su rivista]
Righi, Sara; Forti, Luca; Simonini, Roberto; Ferrari, Valentina; Prevedelli, Daniela; Mucci, Adele
abstract

Increasing evidence in the field of bioprospection fosters the necessity of studying poorly investigated poisonous marine invertebrates to expand knowledge on animal venom biology. Among marine annelids, amphinomid fireworms are notorious for their bearded trunk equipped with a powerful stinging capacity. Here, a methodological workflow based on analytical chemistry techniques (compound isolation followed by mass spectrometry and spectroscopy analyses) was applied to gain new insights, leading to the identification and structural elucidation of an array of natural products from Mediterranean specimens of Hermodice carunculata. Eight betaine-derived unprecedented compounds, named "carunculines", were detected, bearing two terminal ammonium groups tri-and disubstituted at the Cα (A, B) and a series of different alkyl chains (I-VIII). The mixture of chemicals was found in all the body parts of H. carunculata, supporting a mechanism of action triggered by their vehiculation inside the dorsal chaetae, and subsequent injection when chaetae break off on contact. Preliminary investigations to understand adaptive features were also performed, showing a trend in carunculine abundance that fits into the evolutionary history of these worms. These findings shed light on the chemical ecology of amphinomids, giving reasons for the success of H. carunculata in benthic environments and providing promising novel metabolites for biotechnological implications.

2022 - Structural Diversity of Lithium Oligo-α-Pyridylamides [Articolo su rivista]
Raza, A.; Mucci, A.; Nicolini, A.; Cornia, A.
abstract

Lithium oligo-α-pyridylamides are useful intermediates in coordination chemistry. Upon trans-metalation they have afforded a variety of extended metal atom chains (EMACs), which are currently investigated as molecular wires and single-molecule magnets. However, structural information on this class of compounds is scarce. Two trilithium salts of a new, sterically encumbered oligo-α-pyridylamido ligand were isolated in crystalline form and structurally characterized in the solid state and in solution. Lithiation of N2-(trimethylsilyl)-N6-{6-[(trimethylsilyl)amino]pyridin-2-yl}pyridine-2,6-diamine (H3 L) with n-BuLi in thf yielded dimeric adduct [Li6 L2 (thf)6 ] (1), which was crystallized from n-hexane/thf as 1·C6 H14. Crystals of a tetra-thf solvate with formula [Li6 L2 (thf)4 ] (2) were also obtained. The compounds feature two twisted L3− ligands exhibiting a cis-cis conformation and whose five nitrogen donors are all engaged in metal coordination. The six Li+ ions per molecule display coordination numbers ranging from 3 to 5. Compound 1·C6 H14 was investigated by multin-uclear 1D and 2D NMR spectroscopy, including1 H DOSY experiments, which indicated retention of the dimeric structure in benzene-d6 solution. To the best of our knowledge, 1 and 2 are the longest-chain lithium oligo-α-pyridylamides structurally authenticated so far, thereby qualifying as appealing intermediates to access high-nuclearity EMACs by trans-metalation.

2021 - Development of Graphite-Epoxy Composites for Bipolar Plates in PEM Fuel Cells [Abstract in Atti di Convegno]
Roncaglia, Fabrizio; Spinelli, Luca; Imperato, Manuel; Biagi, Roberto; Romagnoli, Marcello; di Bona, Alessandro; Mucci, Adele
abstract

Graphite-Epoxy composites can be a good alternative to metals and metal alloys to build Bipolar Plates (BPs),1 that are important components of Proton Exchange Membrane Fuel Cells (PEMFC), mainly used in hydrogen-powered electric vehicles. We are currently working2 on the preparation of graphite-epoxy composites, suitable for manufacturing BPs meeting the technical targets for 2025.3 Among the overall properties expected for BPs, we are mainly focussing on conductivity, flexural strength and permeability and we are tuning the preparation steps, i.e. composite formulation, mixing and molding, trying to optimize these properties. We compared different resin to filler ratios, dry and wet mixing, mechanical and magnetic stirring and different temperature and pressure ranges. A two-level full factorial Design Of Experiment (DOE) approach was performed to analyze the molding parameters. We observed substantial changes in the properties of the composites, depending on the type of graphite, the mixing method, the epoxy resin to filler ratio and the molding pressure, temperature and time. The results of these studies will be presented.

2021 - Enhanced gold adhesion on sodium alginate films for green electronics: study of the role of oxygenated functional groups [Poster]
Lorenzi, Francesco; Capelli, Raffaella; Mortalò, Cecilia; Mucci, Adele; Parenti, Francesca
abstract

Sodium alginate (SA) is a natural widespread polysaccharide whose constitutional repeating unit is made of alternating mannuronic and guluronic moieties. Transparent, freestanding and flexible films can be obtained from aqueous solutions of SA, making this green polymer very appealing for several uses [1]. When green electronic components are concerned, a thin gold conducting layer with outstanding adhesion can be deposited on SA flexible substrates by sputtering techniques [2]. In fact, as evidenced by a scotch tape test, the adhesion of the metal layer on SA is much stronger than that observed when the thermal evaporation technique is used for Au deposition. To gain insights on the origin of this strong interaction and to understand if it is more of a chemical or physical nature, here we synthesize a series of hydrophobically modified SAs bearing amide or ester groups in place of the carboxyl and/or the hydroxyl groups of the backbone, which are supposed to form complexes with gold. After thoroughly characterization of the polymers, by IR, 1H and 13C NMR spectroscopies, thermogravimetric and elemental analysis, we obtained modified SAs films which were covered whit a thin gold layer by sputtering techniques. [1] X. Guo et al. Int. J. Biol. Macromol. 162 (2020) 618–628. [2] P. Maccagnani et al. Adv. Sustainable Syst. 1900001 (2019).

2021 - Graphite-epoxy composites for fuel-cell bipolar plates: Wet vs dry mixing and role of the design of experiment in the optimization of molding parameters [Articolo su rivista]
Roncaglia, Fabrizio; Romagnoli, Marcello; Incudini, Simone; Santini, Elena; Imperato, Manuel; Spinelli, Luca; di Bona, Alessandro; Biagi, Roberto; Mucci, Adele
abstract

Bipolar plates (BPs) are key components of Proton Exchange Membrane Fuel Cells mainly employed in hydrogen-powered electric vehicles. Here, a reliable and detailed experimental method to prepare graphite-epoxy composites suitable for manufacturing BPs is reported. Dry and wet mixing procedures were compared and a simple composition was optimized, with regard to electrical conductivity. The adoption of wet mixing of the components and the choice of the conductive filler were the main factors that contributed to the achievement of good electrical and mechanical properties. The addition of a small percentage of carbon black as a secondary filler was also advantageous. The effects of molding parameters (pressure, temperature, and time) on a graphite-epoxy composite of fixed-composition were modeled using a Design Of Experiments approach, which provided valuable information for future improvements. Conductivity values well above the US DOE requirements were obtained

2021 - Graphite/epoxy composite for building Bipolar Plates [Abstract in Atti di Convegno]
Spinelli, L.; Roncaglia, F.; Biagi, R.; di Bona, A.; Romagnoli, M.; Mucci, A.
abstract

2021 - Integrated metabolomic analysis and cytokine profiling define clusters of immuno-metabolic correlation in new-onset psoriasis [Articolo su rivista]
Tarentini, Elisabetta; Odorici, Giulia; Righi, Valeria; Paganelli, Alessia; Giacomelli, Luca; Mirisola, Valentina; Mucci, Adele; Benassi, Luisa; D’Aversa, Elisabetta; Lasagni, Claudia; Kaleci, Shaniko; Reali, Eva; Magnoni, Cristina
abstract

The association between the metabolic profile and inflammatory cytokines in psoriasis is poorly understood. We analyzed the metabolic and cytokine/chemokine profiles in serum and skin from patients with new-onset psoriasis and healthy subjects (n = 7/group) by HR-MAS NMR and Bio-Plex immunoassay. Immuno-metabolic correlation matrix was analyzed in skin and serum to identify a potential immune-metabolic signature. Metabolomics analysis showed a significant increase in ascorbate and a decrease in scyllo-inositol, and a trend towards an increase in eight other metabolites in psoriatic skin. In serum, there was a significant increase of dimethylglycine and isoleucine. In parallel, psoriatic skin exhibited an increase of early inflammatory cytokines (IL-6, IL-8, TNF-α, IL-1β) and correlation analysis highlighted some major clusters of immune-metabolic correlations. A cluster comprising scyllo-inositol and lysine showed correlations with T-cell cytokines; a cluster comprising serine and taurine showed a negative correlation with early inflammatory cytokines (IL-6, G-CSF, CCL3). A strong positive correlation was enlightened between glutathione and inflammatory cytokines/angiogenesis promoters of psoriasis. The integration of metabolic and immune data indicated a molecular signature constituted by IL-6, IL1-ra, DMG, CCL4, Ile, Gly and IL-8, which could discriminate patients and healthy subjects and could represent a candidate tool in the diagnosis of new-onset psoriasis.

2021 - Metabolomic analysis of actinic keratosis and scc suggests a grade-independent model of squamous cancerization [Articolo su rivista]
Righi, V.; Reggiani, C.; Tarentini, E.; Mucci, A.; Paganelli, A.; Cesinaro, A. M.; Mataca, E.; Kaleci, S.; Ferrari, B.; Meleti, M.; Magnoni, C.
abstract

Background—Actinic keratoses (AKs) are the most common sun-induced precancerous lesions that can progress to squamocellular carcinoma (SCC). Recently, the grade-independent association between AKs and SCC has been suggested; however, the molecular bases of this potential association have not been investigated. This study has assessed the metabolomic fingerprint of AK I, AK II, AK III and SCC using high resolution magic angle spinning (HR-MAS) nuclear magnetic resonance (NMR) spectroscopy in order to evaluate the hypothesis of grade-independent association between AK and SCC. Association between AKs and SCCs has also been evaluated by histopathology. Methods—Metabolomic data were obtained through HR-MAS NMR spectroscopy. The whole spectral profiles were analyzed through multivariate statistical analysis using MetaboAnalyst 5.0. Histologic examination was performed on sections stained with hematoxylin and eosin; statistical analysis was performed using STATA software version 14. Results—A group of 35 patients affected by AKs and/or SCCs and 10 healthy controls were enrolled for metabolomics analysis. Histopathological analysis was conducted on 170 specimens of SCCs and AKs (including the ones that underwent metabolomic analysis). SCCs and AK I were found to be significantly associated in terms of the content of some metabolites. Moreover, in the logistic regression model, the presence of parakeratosis in AKs appeared to be less frequently associated with SCCs, while AKs with hypertrophy had a two-fold higher risk of being associated with SCC. Conclusions—Our findings, derived from metabolomics and histopathological data, support the notion that AK I are different from healthy skin and share some different features with SCCs. This may further support the expanding notion that all AKs should be treated independently from their clinical appearance or histological grade because they may be associated with SCC.

2021 - Self-Assembled Structures from Solid Cd(II) Acetate in Thiol/Ethanol Solutions: a Novel Type of Organic Chemical Garden [Articolo su rivista]
Bernini, Fabrizio; Castellini, Elena; Sebastianelli, Lorenzo; Bighi, Beatrice; Ignacio Sainz-Díaz, Claro; Mucci, Adele; Malferrari, Daniele; Ranieri, Antonio; Franca Brigatti, Maria; Borsari, Marco
abstract

Cd(II) acetate in tablet form, immersed in ethanol solutions with a high concentration of heptanethiol (30-80 mM) was able to develop self-assembled sail-shaped structures. The solution in which the self-assembled structure is formed is totally organic (both solute and solvent), thus representing a unique case among organic Chemical Gardens. The constituting material for this new Chemical Garden (CG) is made of a single phase, namely a cadmium heptanethiolate with a microcrystalline structure consisting of a central cluster [CdnSn]. The morphological and structural features were studied using different techniques (SEM-EDS, elemental analysis, FT-IR, 113Cd MAS NMR, XRPD). A crystalline cell for the Cd(II) heptanethiolate cluster was obtained that completely differs from that of the solid phase precipitated by mixing an ethanol solution of Cd(II) acetate with heptanethiol. It follows that the conditions under which the formation of Cd(II) thiolate occurs (slowly from solid, quickly from solution) play a critical role in determining the nature and structure of the precipitating phase.

2021 - Serum metabolic signature of binge-like palatable food consumption in female rats by nuclear magnetic resonance spectroscopy [Articolo su rivista]
Cifani, Carlo; Alboni, Silvia; Mucci, Adele; Benatti, Cristina; Botticelli, Luca; Brunello, Nicoletta; Micioni Di Bonaventura, Maria Vittoria; Righi, Valeria
abstract

Maladaptive eating behavior is a growing public health problem and compulsively eating excessive food in a short time, or binge eating, is a key symptom of many eating disorders. In order to investigate the binge-like eating behavior in female rats, induced by intermittent food restrictions/refeeding and frustration stress, we analyzed for the first time the metabolic profile obtained from serum of rats, through nuclear magnetic resonance (NMR) spectroscopy. In this experimental protocol, rats were exposed to chow food restricting/refeeding and frustration stress manipulation. This stress procedure consists of 15 min exposure to the odor and sight of a familiar chocolate paste, without access to it, just before offering the palatable food. In this model, a "binge-eating episode" was considered the significantly higher palatable food consumption within 2 h in restricted and stressed rats (R + S) than in the other three experimental groups: rats with no food restriction and no stress (NR + NS), only stressed rats (NR + S) or only restricted rats (R + NS). Serum samples from these four different rat groups were collected. The statistical analysis of the 1 H NMR spectral profiles of the four sets of samples pointed to O- and N-acetyl glycoproteins as the main biomarkers for the discrimination of restriction effects. Other metabolites, such as threonine, glycine, glutamine, acetate, pyruvate and lactate, showed trends that may be useful to understand metabolic pathways involved in eating disorders. This study suggested that NMR-based metabolomics is a suitable approach to detect biomarkers related to binge-eating behavior.

2021 - Stereoisomerism in Tetrametallic Propeller-like Complexes: a Solid-state and Solution NMR Study on a Tetragallium(III) Derivative [Articolo su rivista]
Cornia, Andrea; Mucci, Adele; Briganti, Matteo; Bridonneau, Nathalie; Nava, Andrea; Nicolini, Alessio
abstract

Tetragallium(III) complex in [Ga4(L4-Py)2(dpm)6]•EtOH, with H3L4-Py = 2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol and Hdpm = dipivaloylmethane, was investigated as a diamagnetic analogue of tetrametallic, propeller-like single-molecule magnets (SMMs). The chiral molecular structure partitions the six CH2 protons of each (L4-Py)3- tripodal ligand into two diastereotopic sets. The two signals were clearly detected by 1H NMR spectroscopy in C6D6, proving that Λ and Δ enantiomers interconvert slowly over NMR timescale. Density functional theory calculations provided quantitative agreement with the observed values of chemical shifts and scalar coupling constants across both geminal and long-range interaction pathways. The solid-state structure suggests the occurrence of a lower symmetry stereoisomer (27 mol%), which was clearly identified in the NMR spectra. Since Fe3+ forms distinctly more inert complexes than Ga3+, comparable or greater configurational stability is expected for the isostructural FeIII4, FeIII3CrIII, and FeIII3VIII SMMs, which are difficult to investigate by solution NMR because of the strong paramagnetism.

2021 - The Copper Chemical Garden as a Low Cost and Efficient Material for Breaking Down Air Pollution by Gaseous Ammonia [Articolo su rivista]
Castellini, Elena; Bernini, Fabrizio; Sebastianelli, Lorenzo; Bighi, Beatrice; Ignacio Sainz-Diaz, Claro; Mucci, Adele; Malferrari, Daniele; Ranieri, Antonio; Gorni, Giulio; Marini, Carlo; Brigatti, Maria Franca; Borsari, Marco
abstract

Chemical garden (CG) from copper(II) sulfate, nitrate and chloride (CG CuSO4, CG Cu(NO3)2, CG CuCl2) were grown and characterized from the structural and compositional point of view using scanning electron microscopy, X-ray powder diffraction, elemental analysis, thermogravimetric analyses coupled with mass spectrometry, and DR (Diffuse Reflectance) UV-Vis-Nir spectroscopy. The main crystalline phases, controlled by the anion of the starting salt, were brochantite and kobyashevite for CG CuSO4, gerhardtite, rouaite and anthonyite for CG Cu(NO3)2, and atacamite for CG CuCl2. The materials were then exposed to ammonia vapors to test the effectiveness of their entrapping property. All materials proved to be very efficient and rapid in the uptake of ammonia which invariably results in the formation of a Cu(II)/NH3 complex. However, after a few tens of minutes, CG Cu(NO3)2 and CG CuCl2 release water and get wet, thereby resulting unsuitable for applications. Only CG CuSO4 keeps dry for at least 25 hours. This makes it a valid candidate for building devices for trapping ammonia and possibly other gases capable of interacting with Cu (II). The entrapment of ammonia by this material was also characterized by 1H and 29Si MAS-NMR XAS spectroscopies.

2020 - A contribution to the harmonization of non-targeted NMR methods for data-driven food authenticity assessment [Articolo su rivista]
Gallo, V.; Ragone, R.; Musio, B.; Todisco, S.; Rizzuti, A.; Mastrorilli, P.; Pontrelli, S.; Intini, N.; Scapicchio, P.; Triggiani, M.; Pascazio, A.; Cobas, C.; Mari, S.; Garino, C.; Arlorio, M.; Acquotti, D.; Airoldi, C.; Arnesano, F.; Assfalg, M.; Barison, A.; Benevelli, F.; Borioni, A.; Cagliani, L. R.; Casadei, L.; Marincola, F. C.; Colson, K.; Consonni, R.; Costantino, G.; Cremonini, M. A.; Davalli, S.; Duarte, I.; Guyader, S.; Hamon, E.; Hegmanns, M.; Lamanna, R.; Longobardi, F.; Mallamace, D.; Mammi, S.; Markus, M.; Alencar Menezes, L. R.; Milone, S.; Molero-Vilchez, D.; Mucci, A.; Napoli, C.; Rossi, M. C.; Sáez-Barajas, E.; Savorani, F.; Schievano, E.; Sciubba, F.; Sobolev, A.; Takis, P. G.; Thomas, F.; Villa-Valverde, P.; Latronico, M.
abstract

Spectroscopic non-targeted methods are gaining ever-growing importance in quality control and authenticity assessment of food products because of their strong potential for identification of specific features of the products by data-driven classifiers. One of the factors hampering the diffusion of spectroscopic non-targeted methods and data-driven classifiers is the lack of harmonized guidelines for their development and validation. In particular, to date, neither conditions to directly compare spectra recorded by different spectrometers nor studies demonstrating the statistical equivalence of the spectra are available. Among the spectroscopic analytical techniques suitable for the development of non-targetedmethods, nuclear magnetic resonance (NMR) offers the unique opportunity to generate statistically equivalent signals. In this paper, the feasibility of NMR spectroscopy to generate statistically equivalent NMR signals from a number of different spectrometers was demonstrated for complex mixtures (aqueous extracts of wheat and flour) by organizing an inter-laboratory comparison involving 36 NMR spectrometers. Univariate statistics along with multivariate analysis were exploited to establish unbiased criteria for assessing the statistical equivalence of the NMR signals. The aspects affecting the signal equivalence were investigated, and possible solutions to reduce the extent of the human error were proposed and applied with satisfactory results. This study furnishes the scientific community with an appropriate and easy procedure to validate non-targeted NMR methods and provides error values to be used as a reference for future studies

2020 - A metabolomic data fusion approach to support gliomas grading [Articolo su rivista]
Righi, V.; Cavallini, N.; Valentini, A.; Pinna, G.; Pavesi, G.; Rossi, M. C.; Puzzolante, A.; Mucci, A.; Cocchi, M.
abstract

Magnetic resonance imaging (MRI) is the current gold standard for the diagnosis of brain tumors. However, despite the development of MRI techniques, the differential diagnosis of central nervous system (CNS) primary pathologies, such as lymphoma and glioblastoma or tumor-like brain lesions and glioma, is often challenging. MRI can be supported by in vivo magnetic resonance spectroscopy (MRS) to enhance its diagnostic power and multiproject-multicenter evaluations of classification of brain tumors have shown that an accuracy around 90% can be achieved for most of the pairwise discrimination problems. However, the survival rate for patients affected by gliomas is still low. The High-Resolution Magic-Angle-Spinning Nuclear Magnetic Resonance (HR-MAS NMR) metabolomics studies may be helpful for the discrimination of gliomas grades and the development of new strategies for clinical intervention. Here, we propose to use T2-filtered, diffusion-filtered and conventional water-presaturated spectra to try to extract as much information as possible, fusing the data gathered by these different NMR experiments and applying a chemometric approach based on Multivariate Curve Resolution (MCR). Biomarkers important for glioma's discrimination were found. In particular, we focused our attention on cystathionine (Cyst) that shows promise as a biomarker for the better prognosis of glioma tumors.

2020 - A new material based on montmorillonite and Cu(II)-phenanthroline complex for effective capture of ammonia from gas phase [Articolo su rivista]
Castellini, E.; Malferrari, D.; Bernini, F.; Bighi, B.; Mucci, A.; Sainz-Diaz, I. C.; Serrano, A.; Castro, G. R.; Brigatti, M. F.; Borsari, M.
abstract

The intercalation of [Cu(Phen)(H2O)2]2+ (CuPhen) in montmorillonite (Mt) produces a stable hybrid material that is very efficient in removing NH3 from gas phase even at extremely low pressures. The process was studied by elemental analysis, X-ray powder diffraction, thermal analysis coupled with evolved gas mass spectrometry and DR UV–Vis, NMR and X-ray absorption spectroscopy. The adsorption of CuPhen on Mt consists of two consecutive steps. During the first one, CuPhen intercalates alone into Mt through a cation exchange process, afterwards CuPhen and SO42− ions entry jointly into the mineral interlayer. The two-steps adsorption process is described by a VI-type isotherm, successfully fitted by two independent Frumkin isotherms. NH3 trapping is long-lasting, easy, fast even at extremely low gas pressure and reversible under mild conditions. Mt containing CuPhen always results well performant in removing ammonia from gas phase, but an appreciably higher adsorption capacity of NH3 is obtained when SO42− ion is absent from the interlayer. This hybrid montmorillonite is thus a promising material to be used in industrial or environmental contexts, as an efficient air-cleaner.

2020 - Potential of wickerhamomyces anomalus in glycerol valorization [Articolo su rivista]
Amaretti, A.; Russo, B.; Raimondi, S.; Leonardi, A.; Foca, G.; Mucci, A.; Zambon, A.; Rossi, M.
abstract

Five-carbons polyalcohols, such as xylitol and arabitol, and microbial oils are important targets for biotechnological industries. Polyalcohols can find application as low-calories sweeteners and as building block in the synthesis of valuable compounds, while lipids are interesting for both biofuel and food industry. The osmophilic yeast Wickerhamomyces anomalus WC 1501 was preliminary known to produce arabitol from glycerol. Production kinetics were investigated in this study. Production was not growth-associated and occurred during a nitrogen-limited stationary phase, in presence of an excess of carbon source. Typical bioreactor batch cultures, carried out with 160 g/L glycerol, yielded 16.0 g/L arabitol in 160 h. A fed-batch process was developed, in which growth is carried out batchwise in a balanced medium containing 20 g/L glycerol, and arabitol production is induced at the entrance into the stationary phase with a pulse of concentrated glycerol to provide the remaining 140 g/L carbon source. At the end of the process 18.0 g/L arabitol were generated. Under these conditions, the yeast also accumulated intracellular triacylglycerols, with fatty acids of 16-18 carbons bearing 0 to 2 unsaturations, reaching up the 23% of biomass dry weight. Therefore, W. anomalus WC 1501 is a good candidate for the development of a fermentative process yielding arabitol and has potential also as oleaginous yeast for producing lipids, further improving the interest in this strain for glycerol biorefinery. The utilization of a fed-batch process allows to carry out distinct growth and production phases and thus allows the optimization of both phases separately, in order to achieve the highest concentration of catalytic biomass during growth and the maximum efficiency during production. This strain deserves further investigation to better exploit its biotechnological potential in the valorization of glycerol.

2020 - Tuning of halobenzenes uptake in montmorillonite from gas phase through a functionalization process involving Cu(II)-phenanthroline and heptanethiol [Articolo su rivista]
Castellini, Elena; Malferrari, Daniele; Bernini, Fabrizio; Bighi, Beatrice; Mucci, Adele; Sainz Diaz, Ignacio Claro; Serrano, Aida; Castro, German R.; Brigatti, Maria Franca; Borsari, Marco
abstract

In this paper, montmorillonite functionalized with a Cu(II)-phenanthroline complex (Mt-CuPhen) and then exposed to heptanethiol vapors (Mt-CuPhen-HPT) was tested for the capture of halobenzenes in gas phase. The treatment of Mt-CuPhen with heptanethiol vapors produced important compositional changes involving Cu(II) reduction, oxidation of thiol to disulfide and dehydration of the mineral interlayer space. Entrapping experiments were carried out on fluorobenzene, chlorobenzene and bromobenzene at 25 and 45°C. The hybrid material proved to be very efficient for all halobenzenes and especially for fluorobenzene. Observed performances are slightly affected by temperature. Halobenzene desorption occurred even at 100°C, a temperature quite lower than that required for decomposition of Mt-CuPhen-HPT. The Mt-CuPhen-HPT hybrid material, therefore, can be reused several times and requires low energy costs for regeneration. An alternative regeneration procedure based on disulfide removal has been proposed as well. Mt-CuPhen-HPT was extensively characterized before and after halobenzenes immobilization through elemental analysis, UV-Vis measurements, thermogravimetric analyses, FTIR, NMR and X-ray absorption spectroscopies.

2019 - EFFECT OF COMPRESSION MOLDING PARAMETERS ON GRAPHITE/EPOXY COMPOSITE BIPOLAR PLATES [Poster]
Roncaglia, Fabrizio; DI BONA, Alessandro; Imperato, Manuel; Biagi, Roberto; Romagnoli, Marcello; Mucci, Adele
abstract

2019 - Field cancerization therapy with ingenol mebutate contributes to restoring skin-metabolism to normal-state in patients with actinic keratosis: a metabolomic analysis [Articolo su rivista]
Righi, V.; Tarentini, E.; Mucci, A.; Reggiani, C.; Rossi, M. C.; Ferrari, F.; Casari, A.; Magnoni, C.
abstract

Actinic keratosis (AK) is a skin premalignant lesion, which progresses into squamous cell carcinoma (SCC) if left untreated. Ingenol mebutate gel is approved for local treatment of non-hyperkeratotic, non-hypertrophic AK; it also has the potential to act as a field cancerization therapy to prevent the progression of AK to SCC. To gain better insights into the mechanisms of ingenol mebutate beyond the mere clinical assessment, we investigated, for the first time, the metabolome of skin tissues from patients with AK, before and after ingenol mebutate treatment, with high-resolution magic angle spinning nuclear magnetic resonance spectroscopy. The metabolomic profiles were compared with those of tissues from healthy volunteers. Overall, we identified a number of metabolites, the homeostasis of which became altered during the process of tumorigenesis from healthy skin to AK, and was restored, at least partially, by ingenol mebutate therapy. These metabolites may help to attain a better understanding of keratinocyte metabolism and to unmask the metabolic pathways related to cell proliferation. These results provide helpful information to identify biomarkers with prognostic and therapeutic significance in AK, and suggest that field cancerization therapy with ingenol mebutate may contribute to restore skin metabolism to a normal state in patients with AK.

2019 - From actinic keratosis to squamous cell carcinoma: NMR analysis with clinical and histological aspects [Abstract in Atti di Convegno]
Righi, Valeria; Tarentini, Elisabetta; Rossi, Maria Cecilia; Magnoni, Cristina; Mucci, Adele
abstract

2019 - INVESTIGATION OF MOLDING PARAMETERS ON GRAPHITE/EPOXY COMPOSITE-BASED BIPOLAR PLATES [Relazione in Atti di Convegno]
Roncaglia, F.; Di Bona, A.; Biagi, R.; Romagnoli, M.; Degrandis, D.; Mucci, A.
abstract

In order to obtain a material suitable for manufacturing bipolar plates for PEM Fuel Cells the effect of molding parameters (pressure, temperature and time), relative to a graphite/epoxy composite of fixed composition, were studied and modeled by means of a two-level full factorial Design Of Experiment approach. In-plane conductivity and mechanical strength were the dependent variables.

2019 - NON CANONICAL CYCLIC NUCLEOTIDES MONOPHOSPHATES IN APHANIZOMENON FLOS-AQUAE: NUCLEAR MAGNETIC RESONANCE AND MASS SPECTROMETRY [Abstract in Atti di Convegno]
Righi, V.; Zambon, A.; Parenti, F.; Rossi, M. C.; Mucci, A.
abstract

Aphanizomenon os-aquae (AFA) cyanobacteria from Klamath Lake (Oregon) are considered a superfood", due to their complete nutritional prole that has proved to have health-enhancing properties. AFA metabolome is quite complex. Here, we present a study that, combining multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry, allows the detection of rather unusual phosphorylated metabolites in AFA. In this study we focused our attention on AFA phosphorylated metabolites giving 31P NMR signals at 20 ppm, a chemical shift that pointed to phosphonates. They instead revealed to be nucleoside 2',3'-cyclic monophosphates (cNMPs), that were characterized by multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry. Our data are fully consistent with the proposed structures and hence demonstrate the presence of cNMPs in AFA, for the rst time. The most studied of these biomolecules is cAMP that activates a protective mechanism in the case of brain tissue injury, whereas it inhibits mitophagy of damaged mitochondria in the kidney.

2019 - Non canonical Cyclic Nucleotides Monophosphates in Aphanizomenon flosaquae: nuclear magnetic resonance and mass spectrometry [Poster]
Righi, Valeria; Zambon, Alfonso; Parenti, Francesca; Rossi, Maria Cecilia; Libertini, Emanuela; Mucci, Adele
abstract

Aphanizomenon flos-aquae (AFA) cyanobacteria from Klamath Lake (Oregon) are considered a “superfood”, due to their complete nutritional profile that has proved to have health-enhancing properties. AFA metabolome is quite complex. Here, we present a study that, combining multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry, allows the detection of rather unusual phosphorylated metabolites in AFA. In this study we focused our attention on AFA phosphorylated metabolites giving 31P NMR signals at 20 ppm, a chemical shift that pointed to phosphonates. They instead revealed to be nucleoside 2’,3’-cyclic monophosphates (cNMPs), that were characterized by multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry. Our data are fully consistent with the proposed structures and hence demonstrate the presence of cNMPs in AFA, for the first time. The most studied of these biomolecules is cAMP that activates a protective mechanism in the case of brain tissue injury, whereas it inhibits mitophagy of damaged mitochondria in the kidney. The role of the other cNMPs there is much to be discovered.

2019 - Non-canonical Cyclic Nucleoside Monophosphates in Aphanizomenon flos-aquae: nuclear magnetic resonance and mass spectrometry [Poster]
Righi, V.; Zambon, A.; Parenti, F.; Rossi, M. C.; Mucci, A.
abstract

Aphanizomenon flos-aquae (AFA) cyanobacteria from Klamath Lake (Oregon) are considered a superfood", due to their complete nutritional prole that has proved to have health-enhancing properties. AFA metabolome is quite complex. Here, we present a study that, combining multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry, allows the detection of rather unusual phosphorylated metabolites in AFA [1,2]. In this study we focused our attention on AFA phosphorylated metabolites giving 31P NMR signals at 20 ppm, a chemical shift that pointed to phosphonates. They instead revealed to be nucleoside 2',3'-cyclic monophosphates (cNMPs), that were characterized by multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry. Our data are fully consistent with the proposed structures and hence demonstrate the presence of cNMPs in AFA, for the rst time. The most studied of these biomolecules is cAMP that activates a protective mechanism in the case of brain tissue injury, whereas it inhibits mitophagy of damaged mitochondria in the kidney [3]. The role of the other cNMPs there is much to be discovered.

2019 - Nucleoside 2’,3’-cyclic monophosphates in Aphanizomenon flos-aquae detected through nuclear magnetic resonance and mass spectrometry [Articolo su rivista]
Zambon, A.; Righi, V.; Parenti, F.; Libertini, E.; Rossi, M. C.; Mucci, A.
abstract

Aphanizomenon flos-aquae (AFA) cyanobacteria from Klamath Lake (Oregon) are considered a “superfood”, due to their broad nutritional profile that has proved to have health-enhancing properties. AFA metabolome is quite complex. Here, we present a study that, combining multinuclear 1H, 31P and 13C Nuclear Magnetic Resonance (NMR) spectroscopy and high-resolution mass spectrometry, led to the detection of uncommon phosphorylated metabolites in AFA. We focused our attention on 31P NMR signals at 20 ppm, a chemical shift that usually points to the presence of phosphonates. The molecules contributing to 20 ppm 31P NMR signals revealed, instead, to be nucleoside 2’,3’-cyclic monophosphates. These metabolites were fully characterized by multinuclear 1H, 31P and 13C NMR spectroscopy and high-resolution mass spectrometry.

2019 - Optoelectronic Properties of A‐π‐D‐π‐A Thiophene‐Based Materials with a Dithienosilole Core: An Experimental and Theoretical Study [Articolo su rivista]
Parenti, Francesca; Caselli, Monica; Vanossi, Davide; Buffagni, Mirko; Imperato, Manuel; Pigani, Laura; Mucci, Adele
abstract

Two A‐π‐D‐π‐A thiophene based small molecules, with a central dithienosilole core and dicyanovinyl end groups were synthesized. These compounds differ only for the presence of alkyl and alkylsulfanyl chains, respectively, on thiophene beta positions. The computational data together with the spectroscopic and electrochemical findings (obtained by means of absorption, steady‐state/time‐resolved emission techniques and cyclic voltammetry) revealed that both molecules possess low electronic and optical band gaps, broad absorption spectra and a good stability both in p and n‐doping states, properties that make them suitable for optoelectronic applications. In either compounds the HOMO‐LUMO transition involves an intramolecular charge transfer from the electron‐donor dithienosilole unit to the two terminal electron‐acceptor DCV groups. A marked positive emission solvatochromism was observed for both molecules and was interpreted on the basis of the symmetry breaking in the S1 excited state. The two synthesized compounds were also compared to their shorter precursors and to similar oligothiophenes to understand how the nature of the building block influences the characteristics of the final materials. Furthermore, it was possible to better understand the contribution of the sulfur atom in modulating the optical properties of the small molecules studied.

2019 - PIN1: a putative molecular target to protect skeletal muscle against age-related muscle loss [Relazione in Atti di Convegno]
Brocca, Lorenza; Grosso, Martina; Pezzini, Camilla; Semeghini, Valentina; Baruffaldi, Fiorenza; Dolfini, Diletta; Mucci, Adele; Righi, Valeria; Lorenzo Puri, Pier; Battini, Renata; Bottinelli, Roberto; Antonietta Pellegrino, Maria; Molinari, Susanna
abstract

Aging is associated with a progressive loss in skeletal muscle mass and strength, known as sarcopenia. Sarcopenia results in a decrease in mobility and an increased risk of developing chronic metabolic disease, thus it represents a major socio-economical problem. Age-related muscle loss cannot be consistently prevented by physical therapy and a pharmacologic therapy does not exist, probably because the molecular basis of this condition is still largely unknown. Many factors such as mitochondrial dysfunction, oxidative stress, inflammation, changes in the innervation of muscle fibers probably play an important role in age-related muscle decline. PIN1 is a widely expressed Peptydyl Prolyl cis/trans isomerase, involved in post-phosphorylation control of the function of multiple target proteins. Many evidences indicate that PIN1 controls signaling pathways involved in skeletal muscle wasting. Our results indicate that skeletal muscle of Pin1 KO mice is protected against muscle loss and weakness during aging. At the molecular level, we found 1) an increased expression of Peroxisome proliferator-activated receptor gamma coactivator 1-alpha (PGC1α), a transcription factor that promotes mitochondrial biogenesis, in skeletal muscle of Pin1 KO mice. Coherently with their resistance to muscle loss, we also found 2) an increase in the expression of the protein synthetic signaling proteins p70 ribosomal S6 kinase (S6K) and of its phosphorylated form in aged skeletal muscle of Pin1 KO mice compared to the wild type controls, suggesting that in these mice protein synthesis is maintained efficient. We also found 3) a significant decrease of Myostatin levels in skeletal muscle of aged Pin1 KO mice. It is well known that Myostatin is upregulated sarcopenia, it activates SMAD2/3 signaling and contributes to protein degradation and muscle atrophy. The transcriptional effects of Pin1 depletion on PGC1α and S6K genes must be mediated by a transcription factor. A putative candidate to mediate these effects is represented by the transcription factor Myocyte Enhancer Factor 2C (MEF2C), a known PIN1 target. In skeletal muscle cells a specific splice variant of MEF2C, MEF2C α1, activates the increase of skeletal muscle mass by activating the expression of IGF1 and S6K. These activities are repressed by its phosphorylation, that renders it a target for the inhibitory effect of PIN1 on its protein stability and activity. Coherently with these premises, we found 4) a decrease of MEF2C protein phosphorylation levels in aged KO mice compared to the control animals. This might at least partially contribute to the increased expression of PGC1α and of S6K. Our results indicate that PIN1 could represent a valuable pharmacological target to counteract age-related muscle loss, simultaneously modulating multiple targets in a concerted way.

2019 - Salivary 1H-NMR Metabolomics in Primary Sjögren Syndrome. Preliminary Results of a Pilot Case-Control Study [Abstract in Rivista]
Setti, G.; Sandri, G.; Tarentini, E.; Panari, L.; Mucci, A.; Righi, V.; Meleti, M.; Magnoni, C.; Consolo, U.; Bellini, P.
abstract

2019 - Structural properties of adsorbent phyllosilicates rule the entrapping ability of intercalated iron-phenanthroline complex towards thiols [Articolo su rivista]
Castellini, E.; Malferrari, D.; Bernini, F.; Mucci, A.; Borsari, M.; Brigatti, M. F.
abstract

The interaction of volatile organic sulfur derivatives, such as 1-heptanethiol (C7H16S), with clay minerals treated with a μ-oxo Fe3+-phenanthroline 1:1 complex results strongly affected by crystal chemical properties of pristine mineral phases. In particular, two sepiolite clays with different structural features demonstrated significantly different ability to immobilize the Fe3+-phenanthroline complex at two pH values (pH = 5.4 and pH = 2.3). The most effective binding was obtained with sepiolite with higher structural disorder at pH 5.4. Accordingly, the resulting hybrid material showed also the greatest efficiency in removal of thiol in gas phase. A direct correlation can be established between the adsorption of the Fe3+-phenanthroline complex and the gas binding process at room temperature. In fact, 1-heptanethiol entrapping occurs via redox reactions between Fe3+ and a first thiol molecule to give the reduced Fe2+-phenanthroline complex and disulfide, followed by the binding of further thiols to the reduced metal centre. The extremely high amount of thiol immobilized by the hybrid material also suggests the co-presence of a catalytic mechanism that guarantees the reoxidation of Fe+2 to Fe+3 and the restoration of redox reactions with thiol. Investigation and conclusions were supported by the several experimental techniques: elemental analysis, X-ray powder diffraction analyses, UV–Vis measurements, FT-IR and NMR spectroscopies, thermogravimetric analyses.

2019 - Structure Model and Toxicity of the Product of Biodissolution of Chrysotile Asbestos in the Lungs [Articolo su rivista]
Gualtieri, A. F.; Lusvardi, G.; Pedone, A.; Di Giuseppe, D.; Zoboli, A.; Mucci, A.; Zambon, A.; Filaferro, M.; Vitale, G.; Benassi, M.; Avallone, R.; Pasquali, L.; Lassinantti Gualtieri, M.
abstract

Asbestos is a commercial term indicating six natural silicates with asbestiform crystal habit. Of these, five are double-chain silicates (amphibole) and one is a layer silicate (serpentine asbestos or chrysotile). Although all species are classified as human carcinogens, their degree of toxicity is still a matter of debate. Amphibole asbestos species are biopersistent in the human lungs and exert their chronic toxic action for decades, whereas chrysotile is not biopersistent and transforms into an amorphous silica structure prone to chemical/physical clearance when exposed to the acidic environment created by the alveolar macrophages. There is evidence in the literature of the toxicity of chrysotile, but its limited biopersistence is thought to explain the difference in toxicity with respect to amphibole asbestos. To date, no comprehensive model describing the toxic action of chrysotile in the lungs is available, as the structure and toxic action of the product formed by the biodissolution of chrysotile are unknown. This work is aimed at fulfilling this gap and explaining the toxic action in terms of structural, chemical, and physical properties. We show that chrysotile's fibrous structure induces cellular damage, mainly through physical interactions. Based on our previous work and novel findings, we propose the following toxicity model: inhaled chrysotile fibers exert their toxicity in the alveolar space by physical and biochemical action. The fibers are soon leached by the intracellular acid environment into a product with residual toxicity, and the dissolution process liberates toxic metals in the intracellular and extracellular environment.

2019 - Sulfur bearing and aromatic compound trapping by layered silicates: a great start for innovative technological applications [Abstract in Atti di Convegno]
Malferrari, D.; Bernini, F.; Bighi, B.; Borsari, M.; Brigatti, M. F.; Castellini, E.; Mucci, A.; Sebastianelli, L.
abstract

2019 - Trapping at the Solid-Gas Interface: Selective Adsorption of Naphthalene by Montmorillonite Intercalated with a Fe(III)-Phenanthroline Complex [Articolo su rivista]
Castellini, E.; Malferrari, D.; Bernini, F.; Sainz Diaz, C. I.; Mucci, A.; Sola, M.; Brigatti, M. F.; Borsari, M.
abstract

In this study, stable hybrid materials (Mt-Fe(III)Phen), made by the μ-oxo Fe(III)-phenanthroline complex [(OH 2 ) 3 (Phen)FeOFe(Phen)(OH 2 ) 3 ] 4+ (Fe(III)Phen) intercalated in different amounts into montmorillonite (Mt), were used as a trap for immobilizing gaseous benzene and naphthalene and their mono chloro-derivatives at 25 and 50 °C. The entrapping process was studied through elemental analysis, magic angle spinning NMR spectroscopy, thermal analysis, and evolved gas mass spectrometry. Naphthalene and 1-chloronaphthalene were found to be immobilized in large amount at both temperatures. Molecular modeling allowed designing of the structure of the interlayer in the presence of the immobilized aromatic molecules. Adsorption is affected by the amount of the Fe complex hosted in the interlayer of the entrapping hybrid materials. On the contrary, under the same conditions, benzene and chlorobenzene were not adsorbed. Thermal desorption of naphthalenes was obtained under mild conditions, and immobilization was found to be reversible at least for 20 adsorption/desorption cycles.

2018 - Analisi metabolomica di tessuti, cellule e biofluidi tramite risonanza magnetica nucleare [Poster]
Mucci, Adele; Cocchi, Marina; Cavallini, Nicola; Righi, Valeria
abstract

Il poster riporta esempi di applicazione della chemiometria all'elaborazione delle informazioni sul metaboloma, ottenute tramite risonanza magnetica nucleare ad alta risoluzione sui tessuti tal quali

2018 - Experimental and Theoretical Investigation of Intercalation and Molecular Structure of Organo-Iron Complexes in Montmorillonite [Articolo su rivista]
Sainz-Díaz, C. I.; Bernini, F.; Castellini, E.; Malferrari, D.; Borsari, M.; Mucci, A.; Brigatti, M. F.
abstract

The intercalation of the μ-oxo Fe(III)-phenanthroline 1:1 complex [(OH2)3(Phen)FeOFe(Phen)(OH2)3]+4 inside montmorillonite yielded a nanostructured material with strong and selective entrapping ability toward thiol molecules and hydrogen sulfide. In this work, experiments and computational molecular modeling by means of quantum mechanical calculations has been applied to study the molecular structure and interactions between this complex and the interlayer of montmorillonite. This approach allowed the identification of the geometrical disposition of the complexes inside the interlayer, the characterization of the hydration and coordination water molecules, and the explanation of the physico-chemical properties of these functionalized materials. The antiferromagnetic spin configuration of the Fe(III) ions results in the most stable state. Two conformers of the complex have been considered, having the phenanthroline rings in twisted or in parallel planes, respectively, and the transition of one conformer into the other has been explored by molecular dynamics simulations. The conformer with phenanthroline rings in parallel planes is found to be the favored species for intercalation in montmorillonite. Both experimental nuclear magnetic resonance analysis and adsorption isotherms are consistent with the modeling results. Different complex amount, equal and double of the cation exchange capacity (CEC) of montmorillonite, and hydration states inside the interlayer have been investigated reproducing faithfully the experimental d(001) spacing of the montmorillonite in the different conditions. The complex molecules intercalated over the CEC of montmorillonite adopt a disposition of the phenanthroline rings perpendicular to that of the complex already introduced by cation exchange.

2018 - Spatially Resolved Bioenergetic and Genetic Reprogramming Through the Brain of Rats Bearing Implanted C6 Gliomas As Detected by Multinuclear High-Resolution Magic Angle Spinning and Genomic Analysis [Articolo su rivista]
Righi, Valeria; García-Martín, María-Luisa; Mucci, Adele; Schenetti, Luisa; Tugnoli, Vitaliano; Lopez-Larrubia, Pilar; Cerdán, Sebastián
abstract

We used 1H, 13C HRMAS and genomic analysis to investigate regionally the transition from oxidative to glycolytic phenotype and its relationship with altered gene expression in adjacent biopsies through the brain of rats bearing C6 gliomas. Tumor-bearing animals were anesthetized and infused with a solution of [1-13C]-glucose, and small adjacent biopsies were obtained spanning transversally from the contralateral hemisphere (regions I and II), the right and left peritumoral areas (regions III and V, respectively), and the tumor core (region IV). These biopsies were analyzed by 1H, 13C HRMAS and by quantitative gene expression techniques. Glycolytic metabolism, as reflected by the [3-13C]-lactate content, increased clearly from regions I to IV, recovering partially to physiological levels in region V. In contrast, oxidative metabolism, as reflected by the [4-13C]-glutamate labeling, decreased in regions I-IV, recovering partially in region V. This metabolic shift from normal to malignant metabolic phenotype paralleled changes in the expression of HIF1α, HIF2α, HIF3α genes, downstream transporters, and regulatory glycolytic, oxidative, and anaplerotic genes in the same regions. Together, our results indicate that genetic and metabolic alterations occurring in the brain of rats bearing C6 gliomas colocalize in situ and the profile of genetic alterations in every region can be inferred from the metabolomic profiles observed in situ by multinuclear HRMAS.

2018 - Spin-controlled electrochemistry using chiral electrodes: Effects on water electrolysis [Abstract in Atti di Convegno]
Tassinari, F; Mtangi, W; Banerjee-Ghosh, K; Adelizzi, B; Parenti, F; Vankayala, K; Palmans, A; Jentzsch, Av; Fontanesi, C; Mucci, A; Meijer, E; Naaman, R
abstract

Hydrogen is the ecologically ideal energy vector. Efficient photo-electrochemical production of hydrogen from water could be the optimal solution to the energy storage problems related to renewable sources. However, in the water splitting reaction the electric potential required to initiate the process significantly exceeds the thermodynamic limit. By controlling the spins of the electrons that are transferred from the solution to the anode, and ensuring that they are coaligned, the threshold voltage for the process can in theory be decreased to that of the thermodynamic voltage. In the present study, by using TiO2 anodes coated with chiral materials, we explore what are the effects of having a spin-polarized current on water electrolysis. The spin-polarization arises from exploiting what is known as Chiral Induced Spin Selectivity effect by using chiral molecules as spin filters. When using chiral molecules instead of a non-chiral analogue, the hydrogen production from water is enhanced, the threshold voltage is reduced and the by-product formation of hydrogen peroxide is suppressed.

2018 - Spin-controlled electrochemistry using chiral electrodes: Effects on water electrolysis [Poster]
Tassinari, F.; Mtangi, W.; Banerjee-Ghosh, K.; Adelizzi, B.; Parenti, F.; Vankayala, K.; Palmans, A.; Jentzsch, A. V.; Fontanesi, C.; Mucci, A.; Meijer, E. W.; Naaman, R
abstract

Hydrogen is the ecologically ideal energy vector. Efficient photo-electrochemical production of hydrogen from water could be the optimal solution to the energy storage problems related to renewable sources. However, in the water splitting reaction the electric potential required to initiate the process significantly exceeds the thermodynamic limit. By controlling the spins of the electrons that are transferred from the solution to the anode, and ensuring that they are coaligned, the threshold voltage for the process can in theory be decreased to that of the thermodynamic voltage. In the present study, by using TiO2 anodes coated with chiral materials, we explore what are the effects of having a spin-polarized current on water electrolysis. The spin-polarization arises from exploiting what is known as Chiral Induced Spin Selectivity effect by using chiral molecules as spin filters. When using chiral molecules instead of a non-chiral analogue, the hydrogen production from water is enhanced, the threshold voltage is reduced and the by-product formation of hydrogen peroxide is suppressed. Figure: control of hydrogen peroxide production. UV-vis spectra from the titration of the used electrolyte (Na2SO4) with o-tolidine of bare TiO2 and TiO2 electrodes coated with (A) self-assembled Zn-porphyrins of either achiral (A-Zn) or chiral (S-Zn) and (B) TPyA molecules. (C) When the electrons transfer to the anodes is non spin specific the spins of the unpaired electrons on the two radicals are aligned antiparallel, hence the interaction is on a singlet surface that correlates with the production of hydrogen peroxide (H2O2). (D) When the electron transfer to the anode is spin specific, the spins of the two electrons are aligned parallel to each other, hence the two radicals interact on a triplet surface that forbids the formation of H2O2 and facilitates the production of oxygen in its ground state.

2018 - Thiophene based A-D-A small molecules with a dithienosilole core: synthesis, theoretical calculations and optoelectronic properties [Abstract in Atti di Convegno]
Parenti, Francesca; Buffagni, Mirko; Caselli, Monica; Mucci, Adele; Pigani, Laura; Vanossi, Davide; Zambon, Alfonso
abstract

Polythiophenes are conjugated materials finding application in many optoelectronic devices.1 Recently, much attention has been devoted to oligothiophenes, the shorter analogous compounds of these polymers. These semiconductor materials are structurally well-defined, monodisperse, free of defects and often possess higher polarizability and charge mobility with respect to the corresponding polymers.2 Thiophene-based small molecules3 are well studied as photoactive materials in organic solar cells. In particular, molecules with A-π-D-π-A architecture, formed by a central electron donating building block (D) and two terminal electron accepting groups (A) linked by π-conjugated bridges, show a low energy absorption band making them suitable as active layers in organic solar cells.4,5 Little modifications of the backbone, i.e. by changing the length of the alkyl substituents or the type of the functional groups, will often result in remarkable modification of the band gap and other optical properties. Here, we present the theoretical calculations, the synthesis and the characterization of two A-π-D-π-A small molecules E1 and E2, where the central unit is a dithienosilole, the terminal units are methyldicyanovinyl functionalized thiophene rings and the π-bridges are alkyl or alkylsulfanyl functionalized thiophene rings, respectively. The aim of this research is to study the structural, electronic and optical properties of these molecules to better understand the role of the sulfur atom of the alkylsulfanyl chains and to gain insight on the properties of these materials in view of their application in optoelectronic and photovoltaic devices

2017 - Baseline studies of The Clay Minerals Society Source Clay montmorillonite STx-1b [Articolo su rivista]
Castellini, Elena; Malferrari, Daniele; Bernini, Fabrizio; Brigatti, Maria Franca; Castro, German Rafael; Medici, Luca; Mucci, Adele; Borsari, Marco
abstract

For more than forty years, The Clay Minerals Society has dispensed a set of source clays which have enabled a large number of researchers to work on identical materials. Many of these source clays remained unchanged over the years but, conversely, other clays have gone out of stock and thus were replaced. This was the fate of montmorillonite STx-1a, which was replaced by STx-1b. Although STx-1a and STx-1b share many basic chemical and mineralogical features, some minor differences exist that can affect behavior. A baseline characterization of the source clay STx-1b, which was the objective of this study, was, therefore, necessary to provide researchers a tool useful not only for new investigation but also to compare new results obtained on STx-1b with literature data on STx-1a. This characterization was gained using traditional and advanced methods that include: 1) chemical composition (major and trace elements); 2) cation exchange capacity determination; 3) thermal analyses coupled with evolved gas mass spectrometry; 4) quantitative mineralogical characterization using powder X-ray diffraction and Rietveld-RIR (Reference Intensity Ratio) refinement; 5) X-ray absorption spectroscopy at the Fe K-edge; 6) diffuse reflectance ultraviolet-visible and infrared spectroscopies; 7) 29Si, 27Al, and 1H magic-angle spinning nuclear magnetic resonance measurements. According to this multi-analytical approach, the montmorillonite chemical formula is [4](Si7.753 Al0.247) [6](Al3.281 Mg0.558 Fe0.136 Ti0.024 Mn0.002) [12](Ca0.341 Na0.039 K0.061) O20 (OH)4.

2017 - Comprehension of metabolic disorders in inflammatory and neoplastic hyper-proliferative diseases: a NMR contribution [Abstract in Atti di Convegno]
Righi, 112 V.; Mucci, A.; Tarentini, Elisabetta; Magnoni, C.
abstract

A progression model based on genetic alterations has been proposed for several types of tumors and in skin diseases, the concept of cancerization field involves cluster of genetically altered cells in a chronically photo damaged skin without clinical evidence of neoplastic lesions [1]. Psoriasis is a chronic, inflammatory skin disease associated with significant morbidity and mortality. Cutaneous Squamous Cell Carcinoma (CSCC) is a common skin cancer characterized by malignant proliferation of keratinocytes. CSCC usually arises from precursor lesions such as actinic keratosis (AKs), but can also grow de novo or on chronically inflamed skin. AKs are the most common skin lesion of disordered keratinocyte proliferation in the disease continuum of photo-damaged skin that may lead to invasive CSCC. In addition, patients with psoriasis can be developed AK or CSCC. Exploring the metabolome of cancer, precancerous lesions and inflammatory disease seems to be a parallel and effective way to understand the phenotypic changes associated with cancer progression. Metabolomics could reveal novel cancer biomarkers that might expand our current understanding of the multifactorial disease. Nuclear Magnetic Resonance (NMR) spectroscopy, giving an accurate description of the molecular composition of a human tissue, provides a “fingerprint” of the whole metabolome [2]. Correlations between some metabolites and proliferative markers allow gaining insight into the relationship between cellular proliferation and metabolic changes associated with the presence of tumor and its aggressiveness.

2017 - Discrimination of glioma brain tumor grades through Multivariate Data Analysis on 1H-HR-MAS NMR ex-vivo spectra [Abstract in Atti di Convegno]
Cavallini, N.; Righi, V.; Mucci, A.; Valentini, A.; Cocchi, M.
abstract

Gliomas account for about 40% of total primitive brain tumors, and discrimination between high and low glioma grades is a vital diagnostic decision, determining the most effective treatment and having an important impact on patient management and outcome. In vivo MRS can support the diagnosis of cancer based on MRI, but it can only be used when the molecular markers are well established. Their identification can be derived from the spectroscopic analysis of ex vivo biopsy samples using HR-MAS NMR technique. 45 specimens of brain tissue were obtained from 35 patients diagnosed either with glioma or lymphoma, and analyzed using HR-MAS NMR. With the aim of retrieving as much information as possible, three different pulse sequences were used, giving rise to three spectral datasets. Multivariate data analysis was performed to identify informative metabolites and their interactions. The key goals were: 1) explore the data; 2) integrate the spectra to enhance information retrieval and interpretability; 3) distinguish among glioma grades III and IV. After proper alignment [1], the datasets were explored by Principal Component Analysis (PCA). The spectra were integrated using Multivariate Curve Resolution (MCR, [2]) on selected intervals. MCR is a method able to resolve overlapping peaks and separate them, by extracting their “pure” peak shapes and their relative concentration in each sample. The concentration information was used to produce the interval-resolved data, which are in principle a more compact and cleaner version of the original data [3]. Class-modeling (SIMCA) and Discriminant Analysis (PLS-DA) were finally applied to the interval-resolved data considering each sequence dataset both separately and datafused. The differences in performance were assessed.

2017 - Enhanced Hydrogen Production with Chiral Conductive Polymer-Based Electrodes [Articolo su rivista]
Tassinari, Francesco; Banerjee Ghosh, Koyel; Parenti, Francesca; Kiran, Vankayala; Mucci, Adele; Naaman, Ron
abstract

Efficient photo-electrochemical production of hydrogen from water is the aim of many studies in recent decades. Typically, one observes that the electric potential required to initiate the process significantly exceeds the thermodynamic limit. It was suggested that by controlling the spins of the electrons that are transferred from the solution to the anode, and ensuring that they are coaligned, the threshold voltage for the process can be decreased to that of the thermodynamic voltage. In the present study, by using anodes coated with chiral conductive polymer, the hydrogen production from water is enhanced, and the threshold voltage is reduced, as compared with anodes coated with achiral polymer. When CdSe quantum dots were embedded within the polymer, the current density was doubled. These new results point to a possible new direction for producing inexpensive, environmentally friendly, efficient water-splitting photo-electrochemical cells. (Graph Presented).

2017 - Ex-vivo HR-MAS NMR contribution to the diagnosis of brain tumours [Altro]
Mucci, Adele
abstract

Some results on the role of HR-MAS NMR in the study of brain tumors, both in animal model and in humans, were presented. The changes in tissue metaboloma were deeple investigated through 1H and 13C NMR and statistics.

2017 - NMR Applications in Food Analysis: Part A [Capitolo/Saggio]
Sobolev, Anatoly Petrovich; Mannina, Luisa; Aru, Violetta; Bellomaria, Alessia; Bertocchi, Fabio; Botta, Bruno; Cagliani, Laura Ruth; Caligiani, Augusta; Capozzi, Francesco; Çela, Dorisa; Marincola, Flaminia Cesare; Ciampa, Alessandra; Coco, Laura Del; Consonni, Roberto; Corsaro, Carmelo; Delfini, Maurizio; Tullio, Valeria Di; Fanizzi, Francesco Paolo; Gallo, Vito; Ghirga, Francesca; Gianferri, Raffaella; Girelli, Chiara Roberta; Ingallina, Cinzia; Laghi, Luca; Latronico, Mario; Longobardi, Francesco; Luchinat, Claudio; Mallamace, Domenico; Mammi, Stefano; Mandaliti, Walter; Marini, Federico; Mastrorilli, Pietro; Mazzei, Pierluigi; Miccheli, Alfredo; Micozzi, Alessandra; Milone, Salvatore; Mucci, Adele; Nepravishta, Ridvan; Paci, Maurizio; Palisi, Angelica; Piccolo, Alessandro; Picone, Gianfranco; Proietti, Noemi; Randazzo, Antonio; Righi, Valeria; Rotondo, Archimede; Salvo, Andrea; Savorani, Francesco; Scano, Paola; Schievano, Elisabetta; Sciubba, Fabio; Tenori, Leonardo; Trimigno, Alessia; Turano, Paola; Vasi, Sebastiano; Capitani, Donatella
abstract

Applications of high-resolution NMR in liquid-state and in semi-solid matrices in the analysis of food components and entire food samples are described using examples of different food matrices and different problems related to food safety, traceability, geographical and botanical origin, farming methods, food processing, maturation and ageing, etc. Although NMR has not yet been recognized as an official methodology of food control for the numerous applications of NMR reported in the literature, the potenziality of this methodology also shows as an approach complementary to the other recognized conventional methodologies.

2017 - NMR Applications in Food Analysis: Part B [Capitolo/Saggio]
Proietti, Noemi; Capitani, Donatella; Aru, Violetta; Bellomaria, Alessia; Bertocchi, Fabio; Botta, Bruno; Cagliani, Laura Ruth; Caligiani, Augusta; Capozzi, Francesco; Çela, Dorisa; Marincola, Flaminia Cesare; Ciampa, Alessandra; Coco, Laura Del; Consonni, Roberto; Corsaro, Carmelo; Delfini, Maurizio; Fanizzi, Francesco Paolo; Gallo, Vito; Ghirga, Francesca; Gianferri, Raffaella; Girelli, Chiara Roberta; Ingallina, Cinzia; Laghi, Luca; Latronico, Mario; Longobardi, Francesco; Luchinat, Claudio; Mallamace, Domenico; Mammi, Stefano; Mandaliti, Walter; Mannina, Luisa; Marini, Federico; Mastrorilli, Pietro; Mazzei, Pierluigi; Miccheli, Alfredo; Micozzi, Alessandra; Milone, Salvatore; Mucci, Adele; Nepravishta, Ridvan; Paci, Maurizio; Palisi, Angelica; Sobolev, Anatoly Petrovich; Piccolo, Alessandro; Picone, Gianfranco; Randazzo, Antonio; Righi, Valeria; Rotondo, Archimede; Salvo, Andrea; Savorani, Francesco; Scano, Paola; Schievano, Elisabetta; Sciubba, Fabio; Tenori, Leonardo; Trimigno, Alessia; Turano, Paola; Vasi, Sebastiano; Di Tullio, Valeria
abstract

Applications of low-field NMR relaxometry and NMR-imaging in the analysis of food samples are described using examples of different food matrices and different problems related to food processing, maturation and ageing, authenticity, shelf-life, perishability, etc.

2017 - NMR Methodologies in Food Analysis [Capitolo/Saggio]
Mannina, Luisa; Sobolev, Anatoly Petrovich; Aru, Violetta; Bellomaria, Alessia; Bertocchi, Fabio; Botta, Bruno; Cagliani, Laura Ruth; Caligiani, Augusta; Capozzi, Francesco; Çela, Dorisa; Marincola, Flaminia Cesare; Ciampa, Alessandra; Coco, Laura Del; Consonni, Roberto; Corsaro, Carmelo; Delfini, Maurizio; Tullio, Valeria Di; Fanizzi, Francesco Paolo; Gallo, Vito; Ghirga, Francesca; Gianferri, Raffaella; Girelli, Chiara Roberta; Ingallina, Cinzia; Laghi, Luca; Latronico, Mario; Longobardi, Francesco; Luchinat, Claudio; Mallamace, Domenico; Mammi, Stefano; Mandaliti, Walter; Marini, Federico; Mastrorilli, Pietro; Mazzei, Pierluigi; Miccheli, Alfredo; Micozzi, Alessandra; Milone, Salvatore; Mucci, Adele; Nepravishta, Ridvan; Paci, Maurizio; Palisi, Angelica; Piccolo, Alessandro; Picone, Gianfranco; Proietti, Noemi; Randazzo, Antonio; Righi, Valeria; Rotondo, Archimede; Salvo, Andrea; Savorani, Francesco; Scano, Paola; Schievano, Elisabetta; Sciubba, Fabio; Tenori, Leonardo; Trimigno, Alessia; Turano, Paola; Vasi, Sebastiano; Capitani, Donatella
abstract

Nuclear Magnetic Resonance (NMR) methodologies offer a comprehensive characterization of foodstuffs owing to the possibility to study a sample from different points of view including structural, compositional, functional, morphological etc. aspects. High resolution NMR spectroscopy applied to semi-solid food samples or to extracts in solution is used to determine the foodstuff composition. Here, some features of high resolution NMR methodologies related to food analysis such as quantitative analysis, chemometrics, and use of databases are included. Other NMR methodologies such as relaxometry and imaging described in this chapter give precious information regarding morphology and texture of intact food samples.

2017 - Novel oligothiophenes with reduced HOMO-LUMO band gap for Optoelectonics [Abstract in Atti di Convegno]
Parenti, Francesca; Buffagni, Mirko; Zambon, Alfonso; Caselli, Monica; Vanossi, Davide; Mucci, Adele
abstract

Here we present the synthesis of A-π-D-π-A thiophene-based oligomers (Figure 1); in the design of these materials we incorporated both electron-donor and electron-acceptor groups by having a central donor dithienosilole, two terminal methyldicyanovinyl acceptor groups and two bithienyl units, functionalised with alkyl or alkylsulfanyl chains, as π-bridges.

2017 - Polymers with Alkylsulfanyl Side Chains for Bulk Heterojunction Solar Cells: Toward a Greener Strategy [Articolo su rivista]
Tassinari, Francesco; Libertini, Emanuela; Parenti, Francesca; Mucci, Adele
abstract

The synthesis and properties of three co-polymers obtained through a Knoevenagel poly-condensation are reported. They are soluble in organic solvents, filmable and solvatochromic. They are characterized through GPC, NMR and UV-visible spectroscopies, CV, and AFM. They display some proneness to form π-stacks, broad absorptions up to about 700 nm, HOMO and LUMO energies that fit those of [60]PCBM. The polymers are incorporated in blends with PCBM within BHJ devices. The best results are found for PSCs obtained from P1 (2.7 % PCE). The insertion of alkylsulfanyl chains improves the photovoltaic performances, with respect to those of alkyl-substituted analogous polymers. The Jsc of the devices are greatly enhanced, supporting the employment of (alkylsulfanyl)thienyl units as base units in photoactive materials.

2017 - Water-soluble polythiophenes as efficient charge-transport layers for the improvement of photovoltaic performance in bulk heterojunction polymeric solar cells [Articolo su rivista]
Lanzi, Massimiliano; Salatelli, Elisabetta; Giorgini, Loris; Mucci, Adele; Pierini, Filippo; Di-Nicola, Francesco Paolo
abstract

Water-soluble regioregular poly3-[(6-sodium sulfonate)hexyl]thiophene (PT6S) and poly3-[(6-trimethylammoniumbromide)hexyl]thiophene (PT6N) have been synthesized and employed both as photoactive layers for the assembling of “green” bulk-heterojunction organic solar cells and as charge-collection layers in a cell with “classic” architecture. While the photovoltaic performances obtained with the two aforementioned polymers were lower than the reference cell, their latter use allowed to notably increase the inherent J-V properties, leading to a considerable enhancement in the overall photovoltaic output. The power conversion efficiency of the optimized multilayer BHJ solar cell reached 4.78%, revealing a higher efficiency than the reference cell (3.63%).

2017 - Π‑Stacking Signature in NMR Solution Spectra of Thiophene-Based Conjugated Polymers [Articolo su rivista]
Parenti, Francesca; Tassinari, Francesco; Libertini, Emanuela; Lanzi, Massimiliano; Mucci, Adele
abstract

Studies on conjugated polymers seldom report on their NMR characterization in solution. This paper shows how NMR experiments, both 1H NMR and routine 2D NMR spectra, can help in gaining a further insight into the aggregation behavior of conjugated polymers and could be used to flank the more employed solid-state NMR and other spectroscopy and microscopy techniques in the understanding of the aggregation processes. NMR spectroscopy allows distinguishing, within the class of poorly solvatochromic conjugated polymers, those highly prone to form π-stacked aggregates from the ones that have a low tendency toward π-stacking.

2016 - CONJUGATED POLYMERS FOR PHOTOVOLTAICS: FROM SOLUTION TO SOLID-STATE NMR [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Libertini, Emanuela; Tassinari, Francesco; Schenetti, Luisa
abstract

Conjugated polymers are widely studied for applications in organic electronics.[1] The structural scenery is varied and the properties of polymers and copolymers can change heavily with the structure. The characterization of organic polymers used in organic electronics, and in particular in polymer solar cells (PSCs), is strongly multidisciplinary. It requires expertise within different branches of chemistry and at the border among chemistry, physics and engineering. Here, the contribution of solution NMR to the study of self-aggregation properties of thiophene based conjugated polymers will be presented. NMR findings on polymers in solution appear to be correlated to morphological properties and solvatochromism. Since one of the most actively investigated application of conjugated polymers is as donors in bulk hetero junction PSCs, also some results obtained with solid-state NMR on polymer/fullerene blends will be reported.

2016 - Changes in the NMR Metabolic Profile of Live Human Neuron-Like SH-SY5Y Cells Exposed to Interferon-α2 [Articolo su rivista]
Valeria, Righi; Schenetti, Luisa; Mucci, Adele; Benatti, Stefania; Tascedda, Fabio; Brunello, Nicoletta; Carmine, Pariante M; Alboni, Silvia
abstract

Interferon (IFN)-α2 is an extensively therapeutically used pro-inflammatory cytokine. Though its efficacy in controlling viral replication and tumor cells proliferation, administration of IFN-α2 is often associated with the development of central side effects. Magnetic resonance spectroscopy studies have demonstrated that IFN-α2 administration affects brain metabolism, however the exact nature of this effect is not completely known. We hypothesized that IFN-α2 can affect metabolic activity of human neuron-like SH-SY5Y cells which possess many characteristics of neurons and represent one of the most used models for studying mechanisms involved in neurotoxicity or neuroprotection. To test our hypothesis we have characterized the metabolic signature of live SH-SY5Y, and their conditioned media, after 24 and 72 h of exposure to vehicle or IFN-α2 (100 ng/ml) by using High Resolution-Magic Angle Spinning (HR-MAS) Nuclear Magnetic Resonance (NMR) spectroscopy. Our results revealed that 1) the use of HR-MAS NMR is ideally suitable for the characterization of the metabolic profile of live cells and their conditioned media without extraction procedures; and 2) a 72 h exposure to IFN-α2 increases the level of metabolites involved in maintaining energetic (including creatine and lactate) and osmotic (such as myo-inositol, scyllo-inositol, taurine and glycerophosphorylcholine) balances in neuron-like cells and of metabolic waste products (namely lactate, ethanol and acetate), glycine and glutamine in their growth media. These results may contribute to gain more knowledge about the IFN-α2 induced effect on the brain and support the interpretation of magnetic resonance spectroscopy studies performed in humans.

2016 - Conjugated Polymers for Solar Cells Incorporating the Dithienosilole Unit [Abstract in Atti di Convegno]
Parenti, Francesca; Tassinari, Francesco; Cugini, Alice; Schenetti, Luisa; Morvillo, P.; Ricciardi, R.; Mucci, Adele
abstract

Polymer Solar Cells (PSC) are widely studied as low cost, light weight and flexible alternative to silicon-based solar cells. The polymers suitable for this purpose should possess good solubility and filming properties and extended π-conjugated systems with high absorption coefficients, UV–Vis-NIR spectra ideally matching the solar spectrum, high hole mobility, and HOMO–LUMO energy levels suitable to be coupled with the acceptor species, such as fullerene derivatives. One of the newest monomeric units that can be used to build conjugated polymers for PSC is functionalized dithienosilole. This contribution will deal with the synthesis and properties of two different low band gap copolymers containing dithienosilole alternated to thienothiophene or to substituted bithiophene

2016 - Erratum to: Changes in the NMR Metabolic Profile of Live Human Neuron-Like SH-SY5Y Cells Exposed to Interferon-α2 (J Neuroimmune Pharmacol, 2015, DOI 10.1007/s11481-015-9641-x) [Altro]
Righi, Valeria; Schenetti, Luisa; Mucci, Adele; Benatti, Stefania; Tascedda, Fabio; Brunello, Nicoletta; Pariante, Carmine M.; Alboni, Silvia
abstract

Erratum

2016 - HR-MAS NMR CONTRIBUTION TO THE COMPREHENSION OF METABOLIC DISORDERS IN INFLAMMATORY AND NEOPLASTIC HYPERPROLIFERATIVE DISEASE [Abstract in Atti di Convegno]
Righi, V.; Schenetti, Luisa; Valentini, A.; REGGIANI BONETTI, Luca; Mucci, Adele
abstract

HR-MAS NMR spectroscopy allows the detailed metabolic analysis of whole biopsy samples, of normal and alterated tissues, to be performed. The NMR spectra constitute a “fingerprint” of the whole metabolome. Correlations between some metabolites and proliferative markers allow gaining insight into the relationship between cellular proliferation and the metabolic changes associated with the presence and tumour aggressiveness. Because metabolites represent the downstream expression of genome, transcriptome and proteome, they can closely reflect the phenotype of an organism at a specific time. Analyzing metabolic differences between normal and perturbed pathways could also provide insight into disease prognosis and diagnosis. Metabolomics could reveal novel cancer biomarkers that might expand our current understanding of this multi-factorial disease. The clinical role of proton NMR in the evaluation of brain tumours, as well as breast and prostate cancer, has been under investigation for several years.[1] During last years our interest was focused on metabolism of colonrectal and brain tissues by using the HR-MAS NMR technique. Some results coming for our research on glioma and linfoma brain tumours and the metabolic correlation existing between colorectal cancer and polyps will be presented.

2016 - Mycosporine-like Amino Acids and Other Phytochemicals Directly Detected by High-Resolution NMR on Klamath (Aphanizomenon flos-aquae) Blue-Green Algae [Articolo su rivista]
Righi, Valeria; Parenti, Francesca; Schenetti, Luisa; Mucci, Adele
abstract

This study describes for the first time the use of high-resolution nuclear magnetic resonance (NMR) on Klamath (Aphanizomenon flos-aquae, AFA) blue-green algae directly on powder suspension. These algae are considered to be a "superfood", due to their complete nutritional profile that has proved to have important therapeutic effects. The main advantage of NMR spectroscopy is that it permits the detection of a number of metabolites all at once. The Klamath alga metabolome was revealed to be quite complex, and the most peculiar phytochemicals that can be detected directly on algae by NMR are mycosporine-like amino acids (porphyra-334, P334; shinorine, Shi) and low molecular weight glycosides (glyceryl β-d-galactopyranoside, GalpG; glyceryl 6-amino-6-deoxy-α-d-glucopyranoside, ADG), all compounds with a high nutraceutical value. The presence of cis-3,4-DhLys was revealed for the first time. This molecule could be involved in the anticancer properties ascribed to AFA.

2016 - NMR Contribution to the comprehension of metabolic disorders in inflammatory and neoplastic hyper-proliferative disease [Abstract in Rivista]
Righi, V.; Mucci, Adele; Fazio, Nicola; Magnoni, Cristina
abstract

A progression model based on genetic alterations has been proposed for several types of tumours and in skin, the concept of cancerization field involves cluster of genetically altered cells in a chronically photo damaged skin without clinical evidence of neoplastic lesions1. Cutaneous Squamous Cell Carcinoma (CSCC) is a common skin cancer characterized by malignant proliferation of keratinocytes. CSCC usually arises from precursor lesions such as actinic keratosis (AKs), but can also grow de novo or on chronically inflamed skin. AKs are the most common skin lesion of disordered keratinocyte proliferation in the disease continuum of photodamaged skin that may lead to invasive CSCC. Although there is reason to believe AKs convert to CSCC, there is also some evidence against this. Most AKs do not progress to CSCC. Clinically, some CSCC appear to arise de novo in healthy skin and in support of this, different genetic abnormalities may underlie AKs and CSCC. Exploring the metabolome of cancer and precancerous lesions seems to be a parallel and effective way to understand the phenotypic changes associated with cancer progression. Metabolomics could reveal novel cancer biomarkers that might expand our current understanding of the multi-factorial disease. Nuclear Magnetic Resonance (NMR) spectroscopy, giving an accurate description of the molecular composition of a human tissue provides a “fingerprint” of the whole metabolome.2 Correlations between some metabolites and proliferative markers allow gaining insight into the relationship between cellular proliferation and metabolic changes associated with the presence of tumor and its aggressiveness.

2016 - NMR EVALUATION OF MITOCHONDRIAL DYSFUNCTION IN LOW-PROTEIN DIET IN COLLAGEN VI-RELATED MYOPATHIES [Abstract in Atti di Convegno]
Righi, V.; Mucci, Adele; Pellegrini, Massimo; Merlini, L.; Schenetti, Luisa
abstract

A pilot clinical trial based on nutritional modulation was designed to assess the efficacy of one-year low-protein diet (LPD) in activating autophagy in skeletal muscle of patients affected by COL6/collagen VI-related myopathies. Ullrich congenital muscular dystrophy and Bethlem myopathy are rare inherited muscle disorders caused by mutations of COL6 genes and for which no cure is available yet. Studies in COL6 null mice revealed that myofiber degeneration involves autophagy defects and that forced activation of autophagy results in the amelioration of muscle pathology. Seven adult patients affected by COL6 myopathies underwent a controlled low-protein diet for twelve months and the alterated metabolites pathway was evaluated in blood samples. Safety measures were assessed, including muscle strength, motor and respiratory function, and metabolic parameters. The treatment resulted safe as shown by preservation of lean-fat percentage of body composition, muscle strength and function. Patients displayed a reduction in lactate (ranging from 10% to 60%) and a decrease in acetate serum levels after one year, as revealed by NMR analysis. The reduced concentration of lactate and acetate after LPD suggests an improvement in mitochondrial aerobic energy production through the tricarboxylic acid cycle, with a reduced conversion of pyruvate to lactate. These metabolic changes point to an improved mitochondrial function. The data provide evidence that LPD is able to activate autophagy and is safe and tolerable in patients with COL6 myopathies, indicating autophagy activation as a potential target for therapeutic applications.

2016 - Organizzazione del: XLV National Congress on Magnetic Resonance [Altro]
Mucci, Adele; Righi, V.; Rossi, M. C.; Schenetti, Luisa
abstract

Il XLV National Congress on Magnetic Resonance si è tenuto dal 5 al 7 settembre 2016 presso il Dipartimento di Scienze Chimiche e Geologiche. Hanno partecipato circa 140 persone e diversi relatori stranieri .

2016 - Phytochemicals Directly Detected by High-Resolution NMR on Klamath (Aphanizomenon Flos-Aquae) Blue-Green Algae [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Righi, V.
abstract

Aphanizomenon flos-aquae (AFA) is a wild freshwater unicellular microalga that spontaneously grows in copious amounts in Upper Klamath Lake (OR, USA) a volcanic lake with hot, deep and mineral rich waters. These algae are considered as a “superfood”, due to their complete nutritional profile that has proved to have important therapeutic effects.[1-4] Here we report on the results obtained applying high-resolution NMR directly on AFA powder suspension. Klamath algae metabolome revealed to be quite complex. The most peculiar phytochemicals that can be detected directly on algae by NMR are mycosporine-like amino acids and low molecular weight glyceryl glycosides.

2016 - Poly(Cyanovinylene Phenylene-Co-Thiophene)s For Polymer Solar Cells [Abstract in Atti di Convegno]
Tassinari, Francesco; Parenti, Francesca; Di Nicola, F. P.; Ballarin, B.; Lanzi, M.; Libertini, Emanuela; Mucci, Adele
abstract

We synthetized, using a Knoevenagel polycondensation reaction, three different poly(phenylenecyanovinylene-co-thiophenes) , slightly changing the structure of the thiophene comonomer, to study the effect that these changes can have on the efficiency of photovoltaic devices built using these polymers

2016 - Polymers for application in organic solar cells: Bithiophene can work better than thienothiophene when coupled to benzodithiophene [Articolo su rivista]
Parenti, Francesca; Ricciardi, Rosa; Diana, Rosita; Morvillo, Pasquale; Fontanesi, Claudio; Tassinari, Francesco; Schenetti, Luisa; Minarini, Carla; Mucci, Adele
abstract

The synthesis and characterization of two low band gap copolymers (P1 and P2) incorporating benzo[1,2-b:4,5- b’]dithiophene unit substituted with octylsulfanylthienyl groups (OSBT) are here reported. These materials, designed to be employed in polymer solar cells (PSCs), were obtained from alternating OSBT and bithiophene (P1) or thienothiophene (P2) units. Their structural electrochemical and photophysical properties were investigated. They are thermally stable and soluble in organic solvents from which they easily form films. They also form p-stacks in solution, in film and display a moderate solvatochromism. These polymers were tested with [70]PCBM in bulk-heterojunction (BHJ) PSCs where they act as donor materials and [70]PCBM is the electron acceptor. The best device, obtained using a 1:3 weight ratio for the P1:[70]PCBM blend, shows a PCE around 1.5%. A broad response from 350 to 700 nm is also observed in the external quantum efficiency (EQE) curves, wider for P1 with respect to P2.

2015 - Assessment of freezing effects and diagnostic potential of BioBank healthy and neoplastic breast tissues through HR-MAS NMR spectroscopy [Articolo su rivista]
Righi, Valeria; Schenetti, Luisa; Maiorana, Antonino; Libertini, Emanuela; Bettelli, Stefania Raffaella; Reggiani Bonetti, Luca; Mucci, Adele
abstract

HR-MAS NMR spectroscopy was employed to monitor the metabolic profiles of Modena BioBank breast samples over 1 year of freezing at -80 C. The study includes 22 adult female patients living in Modena and its hinterland, who underwent total mastectomy or quadrantectomy in 2011–2012. Variations occur, especially affecting phosphocholine (PC) and choline. This is not a trivial finding, since many studies base the distinction between neoplastic and healthy tissues or the assessment of tumor grade on the analysis of choline metabolites. Despite the changes observed, we established that the diagnostic power of the HR-MAS NMR spectra of frozen samples is preserved, at least as far as the distinction between neoplastic and healthy samples is concerned. Lactate (Lac), PC, phosphoethanolamine (PE), taurine (Tau), myo-inositol (Myo) and glucose (Glc) are biomarkers that can be used to distinguish healthy from neoplastic tissues, whereas some metabolite ratios, such as Lac ? PE ? Tau/Glc ? Myo, seem to have even higher discrimination potential.

2015 - Characterization of Conducting Polymers for Organic Solar Cells [Abstract in Atti di Convegno]
Parenti, Francesca; Tassinari, Francesco; Fontanesi, Claudio; Schenetti, Luisa; Morvillo, P.; Ricciardi, R.; Diana, R.; Minarini, C.; Lanzi, M.; Mucci, Adele
abstract

Thiophene based copolymers are widely studied as the donor active layer in bulk hetero junction polymer solar cells (PSCs). These copolymers, in some cases formed by an alternating structure of donor/acceptor units, can be fine tuned in their electronic energy levels in order to achieve better power conversion efficiencies values.1 The characterization of organic polymers for application in PSCs, or organic electronics in general, is multidisciplinary in nature, for it requires expertise within different branches of chemistry and at the border among chemistry, physics and engineering.2 As organic chemists, we have to check the structure and properties of these polymers and this is not always trivial. This contribution will be mainly focussed on the NMR characterization of polymers in solution and to the problems arising when aggregation occurs. This is particularly observed when benzodithiophene and thienothiophene (that are among the most popular units) are present in the backbone. NMR findings appear to be strongly correlated to solvatochromism or morphological properties

2015 - Chiral Polythiophenes [Abstract in Atti di Convegno]
Schenetti, Luisa; Libertini, Emanuela; Mucci, Adele; Parenti, Francesca; Tassinari, Francesco
abstract

Polythiophenes (PT) belong to the class of Conducting organic polymers and Conducting organic polymers that possess chirality present some unique opportunities when used as chiral substrates or as chiral electrode materials. The properties of chiral conducting PT can be tunable modifying the functional groups to the polymer backbone) and since these polymers can be formed as particles, membranes or micro- and nanodimensional fibers ,it is possible to design and to develop specific molecular systems for molecular recognition. The chiroptical properties of CCP films were studied under different evaporation conditions. The chiral recognition abilities of CCP are reported and also a new application in the field of spin filter.

2015 - Chiral conductive polymers as spin filters [Abstract in Atti di Convegno]
Tassinari, Francesco; Parenti, Francesca; Mondal, P. C.; Kantor ­‐Uriel, N.; Mathew, S. P.; Naaman, R.; Fontanesi, Claudio; Schenetti, Luisa; Mucci, Adele
abstract

We investigated spin-selective electron transport through poly{[methyl N -(tert-butoxycarbonyl)-S-3- thienyl- L -cysteinate]-cothiophene} (PCT-L)5. Measurements were performed in two configurations: in an electrochemical cell at room temperature or in a solid state device at various temperatures.

2015 - Crocus sativus Petals: Waste or Valuable Resource? The Answer of High-Resolution and High-Resolution Magic Angle Spinning Nuclear Magnetic Resonance [Articolo su rivista]
Righi, Valeria; Parenti, Francesca; Tugnoli, Vitaliano; Schenetti, Luisa; Mucci, Adele
abstract

Intact Crocus sativus petals were studied for the first time by high-resolution magic angle spinning nuclear magnetic resonance (HR-MAS NMR) spectroscopy, revealing the presence of kinsenoside (2) and goodyeroside A (3), together with 3-hydroxy-γ-butyrolactone (4). These findings were confirmed by HR-NMR analysis of the ethanol extract of fresh petals and showed that, even though carried out rapidly, partial hydrolysis of glucopyranosyloxybutanolides occurs during extraction. On the other hand, kaempferol 3-O-sophoroside (1), which is "NMR-silent" in intact petals, is present in extracts. These results suggest to evaluate the utilization of saffron petals for phytopharmaceutical and nutraceutical purposes to exploit a waste product of massive production of commercial saffron and point to the application of HR-MAS NMR for monitoring bioactive compounds directly on intact petals, avoiding the extraction procedure and the consequent hydrolysis reaction.

2015 - Influence of annealing treatments on solution-processed ZnO film deposited on ITO substrate as electron transport layer for inverted polymer solar cells [Articolo su rivista]
Morvillo, P.; Diana, R.; Mucci, Adele; Bobeico, E.; Ricciardi, R.; Minarini, C.
abstract

In thisworkwestudiedtheinfluence oftheannealingtreatmentsofasol–gel derivedZnOelectron transport layerdepositedonITOsubstrate,ontheperformancesofinvertedbulkheterojunctionpolymer solar cellsusingablendofpoly[(4,8-bis-(2-ethylhexyloxy)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt- (4-(2-ethylhexanoyl)-thieno[3,4-b]thiopene)-2,6-diyl] and[6,6]-phenylC71 butyric acidmethylester. Since theannealingtreatmentsneededtocompletetheformationofthesolution-processedZnO film can modify theunderlyingITOelectrode,weanalyzedtheperformanceofthefabricatedcellsintermsofthe properties ofITOandZnO films. WefoundalinearrelationshipbetweenthesheetresistanceoftheITO layerandtheseriesresistanceofthecorrespondingdevice,whichstronglyinfluences the fill factor.The best powerconversionefficiency (7%)undersimulatedAM1.5Gilluminationof100mW/cm2 was achieved forthepolymersolarcellfabricatedusingaZnO film annealedat150 °C foronly5min.Higher annealing temperaturesandtimesincreasethesheetresistanceoftheITOworseningthedeviceper- formances.

2015 - Performance assessment in fingerprinting and multi component quantitative NMR analyses [Articolo su rivista]
Gallo, Vito; Intini, Nicola; Mastrorilli, Piero; Latronico, Mario; Scapicchio, Pasquale; Triggiani, Maurizio; Bevilacqua, Vitoantonio; Fanizzi, Paolo; Acquotti, Domenico; Airoldi, Cristina; Arnesano, Fabio; Assfalg, Michael; Benevelli, Francesca; Bertelli, Davide; Cagliani, Laura Ruth; Casadei, Luca; Marincola, Flaminia Cesare; Colafemmina, Giuseppe; Consonni, Roberto; Cosentino, Cesare; Davalli, Silvia; Pascali, Sandra Angelica De; D'Aiuto, Virginia; Faccini, Andrea; Gobetto, Roberto; Lamanna, Raffaele; Liguori, Francesca; Longobardi, Francesco; Mallamace, Domenico; Mazzei, Pierluigi; Menegazzo, Ileana; Milone, Salvatore; Mucci, Adele; Napoli, Claudia; Pertinhez, Thelma A; Rizzuti, Antonino; Rocchigiani, Luca; Schievano, Elisabetta; Sciubba, Fabio; Sobolev, Anatoly Petrovich; Tenori, Leonardo; Valerio, Mariacristina
abstract

An inter-laboratory comparison (ILC) was organized with the aim to set up quality control indicators suitable for multi component quantitative analysis by nuclear magnetic resonance (NMR) spectroscopy. 36 NMR data sets (corresponding to 1260 NMR spectra) were produced by 30 participants using 34 NMR spectrometers. The calibration line method was chosen for the quantification of a five-component model mixture. Results show that quantitative NMR is a robust quantification tool and that 26 out of 36 data sets resulted in statistically equivalent calibration lines for all considered NMR signals. The performance of each laboratory was assessed by means of a new performance index (named Qp-score) which is related to the difference between the experimental and the consensus values of the slope of the calibration lines. Laboratories endowed with Qp-score falling within the suitable acceptability range are qualified to produce NMR spectra that can be considered statistically equivalent in terms of relative intensities of the signals. In addition, the specific response of nuclei to the experimental excitation/relaxation conditions was addressed by means of the parameter named NR. NR is related to the difference between the theoretical and the consensus slopes of the calibration lines and is specific for each signal produced by a well-defined set of acquisition parameters

2015 - Performance of polymer solar cells with (alkylsulfanyl)bithiophene copolymers [Relazione in Atti di Convegno]
Ricciardi, R.; Morvillo, P.; Diana, R.; Minarini, C.; Mucci, Adele; Parenti, Francesca; Tassinari, Francesco; Schenetti, Luisa
abstract

In this work we report the performances of PSCs realized with the following materials as electron donor: a polymer containing (alkylsulfanyl)bithiophene unit, the poly[4,4’- bis(butylsulfanyl)-2,2’-bithiophene] (PolyM), a copolymer having bis(octylsulfanyl)bithienyl (OSBT) unit alternated with a BDT unit substituted with ethylhexyloxyl groups, the poly[4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophenealt- 4,4’-bis(octylsulfanyl)-2,2’-bithiophene] (PolyS) and a copolymer having OSBT unit alternated with BDT unit substituted with (octylsulfanyl)thienyl groups, the poly{4,8- bis[(5-octylsulfanyl)-2-thienyl]benzo[1,2-b:4,5- b′]dithiophene-alt-4,4’-bis(octylsulfanyl)-2,2’-bithiophene} (PolyA)

2015 - Synthesis Of Low Band-Gap Conjugated Polymers For Application In Solar Cells [Abstract in Atti di Convegno]
Libertini, Emanuela; Morvillo, P.; Mucci, Adele; Tassinari, Francesco; Schenetti, Luisa; Parenti, Francesca
abstract

Polymer solar cells are a fascinating low cost alternative to silicon-based solar cells1 thanks to light weight, mechanical flexibility and processability. The polymers suitable for this purpose should possess good filming and absorption properties (absorption coefficients >105 cm-1 and UV–Vis spectrum ideally matching the solar spectrum)2, high hole mobility, and HOMO–LUMO energy levels suitable to be coupled with the acceptor species3. In this presentation the synthesis of three different low band gap copolymers is reported and discussed. The properties of these materials are compared in order to gain an insight on the molecular structure-performance relationship of the final device

2014 - A DFT COMPUTATIONAL STUDY OF STRUCTURALLY RELATED POLY-THIOPHENES USED IN PHOTOVOLTAIC SYSTEMS [Abstract in Atti di Convegno]
Fontanesi, Claudio; Vanossi, Davide; L., Cigarini; Mucci, Adele; E., Da Como
abstract

The electric properties of a large number of different complex composed systems (with particular focus on interfacial systems) are rationalized within a “Lego-like sum approach” of the electronic properties of the single components. Such a general modelistic approach span extremely different worlds: from Mott-Schottky barrier to Tafel plots in electrochemical systems [1,2]. In particular, in the field of organic semiconductors exploited to assemble photovoltaic devices, the open circuit potential is rationalized on the basis of the reciprocal HOMO LUMO energy differences between the donor and the acceptor partners [3]. Although such an approach seems by far too much crude in its strategy, the straight comparison of HOMO LUMO MOs energy levels, of the donor and acceptor building blocks, is yet the most widespread tools exploited in the modelization of photovoltaic organic based system [4]. In this work a series of seven thiophene based polymers (donors) are considered, whose structure was designed (both by introduction of ring structures of various chemical nature in the polymeric backbone structure – heteropolymers – and also by various lateral alkyl chains) so to suitably tune the electronic properties of the [6,6]-Phenyl C61 butyric acid methyl ester, often addressed as PCBM, (acceptor) and obtained a satisfactory solubility. Examples of the polymers structure are shown in Chart 1. The electronic properties of the mono-, di-, tri-meric oligomer species are reckoned and compared to experimental spectroscopic and electrochemical results.

2014 - ASSESSMENT OF FREEZING EFFECTS AND DIAGNOSTIC POTENTIAL OF BIOBANK HEALTHY AND NEOPLASTIC BREAST TISSUES THROUGH HR-MAS NMR SPECTROSCOPY [Abstract in Atti di Convegno]
Mucci, Adele; Schenetti, Luisa; Maiorana, Antonino; Bettelli, Stefania Raffaella; REGGIANI BONETTI, Luca; V., Righi
abstract

HR-MAS NMR spectroscopy was employed to monitor the metabolic profiles of Modena BioBank breast samples over one year of freezing at -80 °C. The study includes 22 adult female patients living in Modena and its hinterland, who underwent total mastectomy or quadrantectomy in 2011 - 2012. Variations occur, especially affecting phosphocholine and choline. This is not a trivial finding, since many studies base the distinction between neoplastic and healthy tissues or the assessment of tumor grade on the analysis of choline metabolites [1,2]. Despite the changes observed, we established that the diagnostic power of the HR-MAS NMR spectra of frozen samples is preserved, at least as far as the distinction between neoplastic and healthy samples is concerned. Lactate, phosphocholine, phosphoethanolamine, taurine, myo-inositol and glucose are biomarkers that can be used to distinguish healthy from neoplastic tissues, whereas some metabolite ratios, such as Lac+PE+Tau/Glc+Myo, seem to have even higher discrimination potential. Fig. 1. Scores plot of PCA on neoplastic (crosses) vs healthy (triangles) samples. Loadings profiles (right) of PC2 and PC3. References [1]

2014 - EX VIVO HR-MAS NMR, IN VIVO MRS-MRI AND MULTIVARIATE ANALYSIS TO HIGHLIGHT BIOMARKERS IN GLIOMAS [Abstract in Atti di Convegno]
V., Righi; Schenetti, Luisa; A., Valentini; G., Pavesi; L., Nocetti; Cocchi, Marina; Mucci, Adele
abstract

Gliomas account for about 40% of total primitive brain tumors, and discrimination between high and low glioma grade remains a vital diagnostic decision, determining the most effective treatment and having an important impact on patient management and outcome. The ex vivo HR-MAS NMR spectra provide more details about metabolites than in vivo MRS and permits to produce a metabolic picture of the tissues. Accurate biochemical assignment of metabolites will improve our interpretation of HR-MAS data and the translation of NMR tumor biomarkers to in vivo studies. We developed this project on gliomas with the aim to gain a better insight into the discrimination among different grades and subtypes using ex vivo HR-MAS NMR, in vivo MRS, MRI, clinical data, chemometrics and statistical analysis. We performed experiments on 20 specimen from different grade glioma. After a chemometric analysis some small metabolites such as alanine, lactate, myo-inositol and glycine seems to be able to discriminate between high and low grade glioma. The same chemometric analysis was performed on in vivo MR spectrum. A number of metabolites have been identified as potential biomarkers of tumor type; now we need to combine all the in vivo, ex vivo, histological and clinical data to obtain a unique tumor fingerprints. Results gathered from this study should lead to the development of tools that can facilitate the distinction of tumor types and grade that cannot be readily distinguished by histopathology or by routine neuroimaging.

2014 - Effect of the Electric Field on the Structure of a Chiral Conductive Polymer Thin Film [Abstract in Atti di Convegno]
Tassinari, Francesco; Mathew, S. P.; Fontanesi, Claudio; Schenetti, Luisa; Mucci, Adele; Naaman, R.
abstract

The chemical-physical properties of conductive polymer thin films are strictly related to the structure and conformations of the chains in the polymer lattice. Crystallinity, chain length, substituents, doping level are just some of the many variables that play a role in the final properties of the polymer films. Another key factor is the orientation of the chains inside the thin film. A polymer chain is anisotropic, and so are its properties. However, a lattice where the chains are randomly arranged will have the same properties no matter which direction we measure them, whereas an oriented lattice will show different properties related to the preferential order of the macromolecular structure. We used different electric fields to align the macromolecules of a chiral conductive polymer (CCP), capable of self-organizing in chiral helixes in the solid state, and we studied its effect on the anisotropy of the obtained thin films, on the structure of the aggregates and on the conductive properties of the polymer by means of different instrumental techniques. All the measurements showed a preferential alignment of the polymer chains after the process under applied electric field. Circular dichroism was used to probe the chirality of the polymer aggregates, and it was found that the field strongly influences the helical superstructures of the CCP. The use of the electric field to fine tune the helical structures of this chiral polymer stands out as an interesting possibility which we are currently investigating.

2014 - Low band gap polymers for application in solar cells: synthesis and characterization of thienothiophene-thiophene copolymers [Articolo su rivista]
P., Morvillo; R., Diana; Fontanesi, Claudio; R., Ricciardi; M., Lanzi; Mucci, Adele; Tassinari, Francesco; Schenetti, Luisa; C., Minarini; Parenti, Francesca
abstract

In this paper we present the synthesis and characterization of two novel copolymers obtained from a bithiophene unit carrying octylsulfanyl side chains and thienothiophene units substituted with keto (PK) or ester (PE) groups. Their structural, electrochemical and photophysical properties were investigated by gel permeation chromatography (GPC), thermogravimetric analysis (TGA), NMR, UV-visible-NIR spectroscopy, cyclic voltammetry (CV) and atomic force microscopy (AFM). They possess good solubility in common organic solvents, filmability, proneness to form π-stacks, moderate solvatochromism, good thermal stability and low band gap energy. They were tested as donor materials in combination with [70]PCBM (electron acceptor) in bulk-heterojunction polymer solar cells. The geometry of the devices are: glass/ITO/PEDOT:PSS/ copolymer:[70]PCBM/Ca/Al. The external quantum efficiency curve of the best device, realized using a blend of PK:[70]PCBM, 1:2 weight ratio, shows a broad response from 350 to 1000 nm. The power conversion efficiency under 100 mW/cm2 AM 1.5G illumination is greater than 1%.

2014 - NMR and metabolic profile of human, animal, vegetable tissues and cells [Altro]
Mucci, Adele; Schenetti, Luisa; Righi, Valeria
abstract

Giornata di approfondimento sulla risonanza magnetica nucleare applicata alle matrici in oggetto

2014 - Polymer Solar Cells based on Benzodithiophene copolymers [Abstract in Atti di Convegno]
Parenti, Francesca; Diana, R.; Fontanesi, Claudio; Minarini, C.; Morvillo, P.; Ricciardi, R.; Schenetti, Luisa; Tassinari, Francesco; Mucci, Adele
abstract

Polymer solar cells are widely seen as the promise to a cheap alternative to the silicon-based ones. In addition to their low costs, they also have other advantages such as light weight, easy processability and compatibility with large scale flexible substrates, which make them suitable for a wide range of applications. However, the efficiency of photovoltaic energy conversion for these plastic devices is still low and this is limiting their commercial use. The efficiency of these polymeric photovoltaic cells got a significative increase when the bulk heterojunction (BHJ) configuration was introduced: it consists in an interpenetrating network of electron donor and acceptor materials that largely increases the active area and diminishes the distance that charge carriers have to travel. Recently, benzodithiophene (BDT) based polymers (Fig.1) have been used as electron donors in polymer solar cells showing very promising properties such as an increased charge transport and a red shift on the absorption spectra. In this work, the synthesis of different regioregular copolymers having substituted BDT as one of the monomers are described. The obtained polymers are characterized by spectroscopic and electrochemical techniques. Energy conversion measurements of BHJ solar cells produced with these polymers were conducted, and the electrical performances were compared in order to study the influence of the different comonomers on the overall efficiency of the devices.

2014 - Solventless deposition of oligo- and polythiophenes for bulk heterojunction solar cells [Articolo su rivista]
Massimiliano, Lanzi; Francesco Paolo Di, Nicola; Francesco, Errani; Luisa, Paganin; Mucci, Adele
abstract

In this paper we report on the vacuum thermal evaporation (VTE) of poly(3-hexyl)thiophene (P3HT) and a thiophene derivative octamer (OCT) on glassy substrates. The films obtained have been characterized using FT-IR and NMR techniques and, for OCT, UV–vis, XRD and cyclic voltammetry. Solar cells, obtained by simultaneous evaporation of the electron–donor (P3HT or OCT) and electron-acceptor (C60-fullerene) components, were examined by AFM and their efficiency was evaluated under simulated solar illumination. With the oligomeric sample a power conversion efficiency of 1.21% was obtained: a value higher than that obtained with a device prepared with the same oligomer adopting the conventional coating systems used for building-up polymeric BHJ solar cells

2014 - Synthesis and characterization of an organic co-polymer for photovoltaic application [Abstract in Atti di Convegno]
Andrea, Copelli; Tassinari, Francesco; Mucci, Adele; Parenti, Francesca
abstract

Harvesting energy directly from sunlight using photovoltaic technology is considered as being one of the most important ways to address growing global energy needs using a renewable resource. Polymeric solar cells (PSCs) are a promising alternative to silicon-based solar cell for producing clean and renewable energy thanks to light weight, mechanical flexibility, processability and low costs [1]. The most studied polymers are the 3-alkyl substituted polythiophenes, but they show limited efficiency and, to improve power conversion, the synthesis of new systems is required [2]. Co-polymers formed by ThienoThiophene Carboxylate (TTC) and DiThienoSilole (DTS) units are widely studied as Donor systems in Bulk Heterojunction (BHJ) solar cells. In this presentation we report the synthesis of PSiTT (see the chemical structure) and it's characterization via UV-Vis-NIR, NMR Spectroscopy, IR, AFM and GPC.

2014 - Synthesis of low bandgap Thiophene-Based Copolymers: new donor material candidates in organic solar cells [Abstract in Atti di Convegno]
Parenti, Francesca; P., Morvillo; R., Diana; R., Ricciardi; C., Minarini; Fontanesi, Claudio; Mucci, Adele; A., Copelli; Schenetti, Luisa; Tassinari, Francesco
abstract

Polymer solar cells (PSCs) are emerging as promising alternatives to silicon-based solar cells [1] thanks to light weight, mechanical flexibility, processability and low costs. One of the common polymers used in PSCs are 3-alkyl substituted polythiophenes, but a low band gap alternative is needed in order to reach better cell performances [2]. Copolymers bearing thienothiophene (TT) and benzodithiophene (BDT) alternating units are widely studied as donor material in Bulk Heterojunction Cells [3]. In this poster communication we report on the synthesis and spectroscopic electrochemical, photovoltaic characterization of two thiophene based copolymers bearing thienyl substituted-BDT units alternating with bithiophene and TT-units respectively.

2013 - Citron and lemon under the lens of HR-MAS NMR spectroscopy [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Valeria, Righi; Schenetti, Luisa
abstract

High Resolution Magic Angle Spinning (HR-MAS) is an NMR technique that can be applied to semi-solid samples. Flavedo, albedo, pulp, seeds, and oil gland content of lemon and citron were studied through HR-MAS NMR spectroscopy, that was used directly on intact tissue specimens without any physicochemical manipulation. HR-MAS NMR proves to be very immediate in detecting terpenes, sugars, organic acids, aminoacids and osmolites. It is valuable in observing changes in sugars, principal organic acids (mainly citric and malic) and ethanol contents on pulp specimens and this strongly point to its use to follow fruit ripening, or commercial assessment of fruit maturity. HR-MAS NMR was also used to derive the molar percentage of fatty acid components of lipids in seeds, which can change depending on Citrus species and varieties. Finally, this technique was employed to elucidate the metabolic profile of mold flavedo.

2013 - Effect of a Peat Humic Acid on Morphogenesis in Leaf Explants of Pyrus communis and Cydonia oblonga. Metabolomic Analysis at an Early Stage of Regeneration [Articolo su rivista]
Grazia, Marino; Valeria, Righi; Andrea, Simoni; Schenetti, Luisa; Mucci, Adele; Vitaliano, Tugnoli; Enrico, Muzzi; Ornella, Francioso
abstract

Plant regeneration is a critical step in most in vitro breeding techniques. The present paper studies the 21 effects of a low-molecular-weight humic acid (HA) on morphogenesis from pear and quince leaf 22 explants. Variable HA amounts [0 (control), 1, 5, 10 and 20 mg C L-1] were added to the regeneration 23 media. A dose-response effect was observed in pear for root and shoot production; it was improved at 24 HA 1 mg C L-1 and considerably reduced at the highest amounts. HA was, instead, ineffective in 25 quince. The 1H HR-MAS NMR analyses of calli in the induction phase showed more evident 26 metabolite (asparagine, alanine and γ-amino butyric acid) signals in quince than pear. The assignment 27 of overlapped signals in both genotypes were supported by the 2D NMR analyses. Spectroscopic 28 characterization suggested also an enhancement of asparagine contents in morphogenic calli of pear 29 with respect to the control and higher HA amount treatments.

2013 - Electrochemically assisted grafting of asymmetric alkynyl(aryl)iodonium salts on glassy carbon with focus on the alkynyl/aryl grafting ratio [Articolo su rivista]
Florini, Nicola; M., Michelazzi; Parenti, Francesca; Mucci, Adele; Sola, Marco; C., Baratti; De Renzi, Valentina; K., Daasbjerg; S. U., Pedersen; Fontanesi, Claudio
abstract

Glassy carbon (GC) surfaces are functionalized exploiting the electrochemical reduction of asymmetric iodonium salts of the general formula [4-Zsingle bondC6H4single bondI+single bondCtriple bond; length of mdashC(CH2)4Cl, Z = NO2, Br, F, H, or CH3]. The range of Z groups was selected aiming to examine the Carylsingle bondI bond energy as a function of the “electron withdrawing/electron donating” ability of the Z-group, with the ultimate purpose of controlling the alkynyl/aryl grafting ratio. The electroreduction mechanism and the characteristics of the grafted surface are studied by means of cyclic voltammetry and X-ray photoelectron spectroscopy. It is shown that the alkynyl/aryl grafting ratio decreases with the increasing electron withdrawing nature of Z, which induces a weakening of the Carylsingle bondI bond. Ab initio DFT vertical electron affinities (EAv) allowed to rationalize the electroreduction potentials of both the bulk and surface functionalised redox couples. Moreover, the alkynyl/aryl grafting ratio is assessed, at a molecular level, on the basis of ab initio DFT potential energy surfaces.

2013 - Evaluation of the effects of cryopreservation on Modena Biobank tissue samples through HR-MAS NMR [Abstract in Atti di Convegno]
Valeria, Righi; Schenetti, Luisa; Maiorana, Antonino; Bettelli, Stefania Raffaella; REGGIANI BONETTI, Luca; Mucci, Adele
abstract

The application of high-resolution magic angle spinning (HR-MAS) NMR spectroscopy to the analysis of intact tissue biopsies and surgery samples dates back to 1997. It represents, at present, an actively investigated field, and it is used to obtain the metabolic fingerprints of tissues. It has been shown to differentiate between normal and neoplastic tissue in the case of breast, brain, kidney, colon cancer and other malignancies in the upper gastrointestinal tract. Nevertheless, it is difficult to run HR-MAS analysis immediately after surgical resection or biopsy, and samples are currently frozen in liquid nitrogen and then stored to -80 °C. Some studies reporting the effect of sample ischaemia, spinning time and measurement temperature on the metabolic profile of tissues can be found.1 Nevertheless, another important issue to be addressed is the effect of cryopreservation time on the metabolic profile of tissues. Crypreservation represents a more and more common practice, due to the widespread of tissue BioBanks. To gain a deeper insight into metabolic changes that occur during the storage, samples of Modena BioBank were analyzed through HR-MAS NMR after 1, 6 and 12 months from collection. The results of this study were discussed.

2013 - Metabolic characterization of SH-SY5Y cells and effects of interferon-alpha exposure [Abstract in Atti di Convegno]
Alboni, Silvia; Schenetti, Luisa; Mucci, Adele; Brunello, Nicoletta; Valeria, Righi
abstract

The human neuroblastoma SH-SY5Y cell line is a third successive subclone of the SK-N-SH line, originally established from a bone marrow biopsy of a neuroblastoma patient. These cells possess many characteristics of neurons, and they represent one of the most-used models for studying cellular events and mechanisms involved in neurotoxicity and neurodegeneration or even in neuroprotection. Interferons are cytokines endowed with a pleiotropic spectrum of biological properties, including immunomodulation, antiviral and proinflammatory activity. Interferon (IFN)-α is a type I IFN that may have broad-ranging actions in the brain, affecting neuronal differentiation, survival and synaptic plasticity. We previously demonstrated that a 72 hours exposure to IFN-α induces early apoptosis in SH-SY5Y cells. This prompted us to investigate the metabolic profile of the SH-SY5Y cells using HR-MAS NMR Spectroscopy after a 72 hours exposure to IFN-α to explore the metabolic changes that characterize these cells. Moreover, since a metabolic characterization of this extensively used cell clone is still lacking, we analyzed the metabolic profile of the SH-SY5Y in standard growth conditions. Results show some interesting changes in metabolites, such as choline containing compounds, creatine and glutamate. Our goal will be to relate the metabolic changes to IFN-α exposure.

2013 - Regiochemistry in the electrochemical assisted grafting of glassy carbon. With focus on sterical hindrance of lateral chains in the electroreduction process of multi-functionalized bithiophene [Articolo su rivista]
Tassinari, Francesco; Vanossi, Davide; Mucci, Adele; Parenti, Francesca; Fontanesi, Claudio
abstract

The electrochemically assisted grafting process of glassy carbon (GC) surfaces is pursued by using the 7-[(5,50-diiodo-2,20-bithiophen-4-yl)sulfanyl]heptanenitrile (DIBHN). Which is an ad hoc synthesized bithiophene derivative: the DIBHN features two non-equivalent iodine substituents in the 5 (which is under the sterical hindrance of the sulfanylheptanenitrile group) and 50 positions. CV measurements show the occurrence of two reduction processes, the second, more cathodic one, induces the grafting. This result is in qualitative agreement with theoretical calculations (B3LYP/6-311G level of the theory) concerning the comparison of the optimized structures of the DIBHN neutral and radical anion species (first electroreduction process): the C–I bond length of the iodine in the 5 position varies from 2.098 (neutral) to 2.835 Å (radical anion), while the C–I bond length of the iodine in the 50 position remains virtually unchanged when comparing the geometries of the neutral and radical anion structures. Raman spectra are recorded for various polymer film thicknesses; the comparison with theoretical calculated Raman spectra further support the effective grafting of the glassy carbon surface.

2013 - Synthesis and properties of new bio-functionalized polythiophenes [Altro]
Tassinari, Francesco; Fontanesi, Claudio; Mucci, Adele; Schenetti, Luisa
abstract

Polythiophenes are part of the family of conductive polymers. They are extremely popular nowadays for their promising applications in the organic solar cells. Their reactivity is very well established, and a large number of reaction for their modification is available in the literature. The possibility of tailoring these polythiophenes with a large library of different functional groups opens the door to a great number of possible applications. We synthesized two bio-functionalized polythiophenes, one bearing a cysteine aminoacid[1], the other an aniline ring acting as a linker for a laccase enzyme. The presence of the cysteine aminoacid in the side-chain of the polymer backbone gives to the polythiophene a very large circular dichroism activity, and the sign of the effect is related to the chirality of the attached aminoacid. The wavelenght of the CD effect is in the absorption zone of the thiophene rings, which is a strong proof to the presence of helicoidal arrangement of the polymer backbone in the polymer aggregates. The helicoidal structure is promoted by the side-chain aminoacid, and the chirality of the substituent influence the direction of the helix. This chiral conductive polymer and the helical structures that are present in its solid state are a perfect material to study the spin-conduction inside organic molecules (such as the Chiral Induced Spin Selectivity effect). The aniline substituted polymer has been designed to be used for bio-sensing applications. The thiophene substituted monomer is electropolymerized directly on the electrode surface, and the presence of the aniline allows the direct linking of the laccase enzyme to the electrode surface. The laccase enzyme catalyses the oxidation of phenols and polyphenols, and the product of the oxidation can be reduced at the electrode surface to give a signal proportional to the analyte concentration[2]. The same approach can be used for a large range of enzymes, giving this kind of polythiophene-based sensor engineering a wide applicability.

2012 - A nanogap–array platform for testing the optically modulated conduction of gold–octithiophene–gold junction for molecular optoelectronics [Articolo su rivista]
Ismael, Rattalino; Valentina, Cauda; Paolo, Motto; Tania, Limongi; Gobind, Das; Luca, Razzari; Parenti, Francesca; Enzo Di, Fabrizio; Mucci, Adele; Schenetti, Luisa; Gianluca, Piccinini; Danilo, Demarchi
abstract

This paper presents a fully–customized platform for the self–assembling and the electric and spectroscopic testing the light dependent conduction of gold–oligothiophene–gold molecular junctions. The flexibility and novelty of the platform rely on its plug-and-play connection to an external electronic board to perform eight parallel nanogap fabrication by Electromigration Induced Break Junction (EIBJ) and molecular electrical characterization. In addition, the octithiophene molecules are ad-hoc synthesized to efficiently self-assembly and selectively bridge the nanogap electrodes upon deposition, which can be carried out directly and in parallel on the 8 nanogap array platform. The high portability of the platform is well suited for in–situ microscopic and spectroscopic analyses. In particular, we tested the electrical functionality of octithiophene molecular junctions, by coupling electrical current–voltage (I–V) characterization with fluorescence and Raman spectroscopies. In addition, Surface–Enhanced Raman Spectroscopy (SERS) was used for the first time to precisely correlate the position of the molecule with the conductance of the junction. Modulation of the electric conductance can be also achieved by varying the light excitation wavelength. Such electrical transduction of the junction revealed a peak in molecule conduction around light excitation wavelength of 450 nm, with a photoresponsive modulation of the current at low bias voltage up to 120% with respect to the initial value at 300 nm. The proposed ad-hoc platform design makes molecular junctions real working blocks, which can be interfaced with external circuitries to serve the function of electronic components or sensors and overcome the limitations of usability, cost and portability of traditional molecular contacting methods, such as Mechanically Controlled Break Junction (MCBJ) or scanning probe microscopy. We thus demonstrate that the optoelectronic properties of oligothiophenes can be exploited in the form of molecular junctions to fabricate optoelectronic devices for molecular electronics.

2012 - A novel copolymer from benzodithiophene and alkylsulfanyl-bithiophene: Synthesis, characterization and application in polymer solar cells [Articolo su rivista]
P., Morvillo; Parenti, Francesca; R., Diana; Fontanesi, Claudio; Mucci, Adele; Tassinari, Francesco; Schenetti, Luisa
abstract

In this paper we present the synthesis and characterization of a novel copolymer from thienothiophene and bithiophene units carrying nonanoyl and octylsulfanyl side chains, poly[1-(thieno[3,4-b]thien-2-yl)nonan-1-one-alt-4,4’-bis(octylsulfanyl)-2,2’-bithiophene] (PolyH). The structural, electrochemical and photophysical properties of PolyH were investigated by gel permeation chromatography (GPC), thermogravimetric analysis (TGA), NMR, UV-VIS-NIR spectroscopy and cyclic voltammetry (CV). PolyH possesses good solubility in common organic solvents, filmability, a proneness to form π-stacks and a moderate solvatochromism. PolyH was tested as donor material in combination with [70]PCBM (electron acceptor) in bulk-heterojunction polymer solar cells. The geometry of the device is: glass/ITO/PEDOT:PSS/ PolyH:[70]PCBM/Ca/Al. The external quantum efficiency curve of the best device (realized using a blend of PolyH:[70]PCBM, 1:2 weight ratio) shows a broad response from 350 to 1000 nm. The power conversion efficiency under 100 mW/cm2 AM 1.5G illumination is greater than 1%.

2012 - Aggregation behaviour of a water-soluble ammonium-functionalizedpolythiophene: Luminescence enhancement induced by bile-acid anions [Articolo su rivista]
R., Cagnoli; Caselli, Monica; Libertini, Emanuela; Mucci, Adele; Parenti, Francesca; Ponterini, Glauco; Schenetti, Luisa
abstract

The water-soluble poly{trimethyl-[7-(3-thienylsulfanyl)heptyl]ammonium iodide-co-thiophene} (PTNDMe3) forms aggregates whose size span a large range of values, depending on solvent, concentrationand film formation conditions. Larger aggregates were detected by atomic force microscopy and dynamic light scattering, smaller ones by DOSY NMR, UVevisible and fluorescence. All techniques indicate a reduced aggregation of PTNDMe3 in DMSO relative to water and a marked de-aggregation of PTNDMe3 in water following addition of bile-acid anions such as deoxycholate and ursodeoxycholate.The latter effect shows itself through a very large enhancement of the polymer photoluminescence likely caused by disruption of aggregated non-emissive exciton traps. A tailored combination of electrostaticand hydrophobic interactions between the polymer and the bile-acid anions seems to be necessary to achieve this effect. These observations suggest that this polythiophene might provide a basis for the development of fluorescent sensors suitable for the detection of medium-sized amphiphilic biomolecules.

2012 - Applicazioni dell'HR-MAS NMR all'analisi di campioni vegetali [Altro]
Mucci, Adele
abstract

Sono stati presentati a un workshop sulle applicazioni HR-MAS NMR al Politecnico di Milano i risultati preliminari ottenuti su campioni di limone, cedro e crocus sativus.

2012 - Chimica Organica [Traduzione di Libro]
Prati, Fabio; Mucci, Adele; Schenetti, Luisa; Giuseppe, Bifulco; Andrea, Bottoni; Ugo, Chiacchio; Antonino, Corsaro; Brigida, D'Abrosca; Marina Della, Greca; Stefano di, Stefano; Fernando, Formaggio; Marina, Gobbo; Giulia, Licini; Francesca, Marini; Severina, Pacifico; Giovanni, Petrillo; Cristina, Prandi; Riccardo, Salvio; Diego, Savoia; Gianfranco, Scorrano; Cinzia, Tavani; Sergio, Thea
abstract

Testo a livello universitario di Chimica Organica per studenti dei corsi di Farmacia, Chimica, Chimica e Tecnologia Farmaceutiche.

2012 - Ex vivo HR-MAS NMR, in vivo MRS-MRI and Multiivariate analysis to Highlight Biomarkers in Gliomas [Abstract in Atti di Convegno]
Righi, V.; Schenetti, Luisa; Valentini, A.; Nocetti, L.; Pavesi, G.; Tugnoli, V.; Mucci, Adele
abstract

Gliomas account for about 40% of total primitive brain tumors, and discrimination between high and low glioma grade remains a vital diagnostic decision, determining the most effective treatment and having an important impact on patient management and outcome. The in vivo MRS is considered a tool able to help the diagnosis based on MRI in the evaluation of several human pathologies, including cancer. In vivo MRS provides the spectra of living tissues, directly correlated to their chemical composition, but it can be used when the molecular markers of tissues are well established by means of a detailed biochemical picture. This last can be derived from the spectroscopic analysis of ex vivo biopsy samples using High Resolution Magic Angle Spinning (HR-MAS) NMR technique. The ex vivo HR-MAS NMR spectra provide more details about metabolites (aminoacids, carbohydrates, osmolites, organic acids, mobile lipids) than in vivo MRS and permits to produce a metabolic picture of the tissues. Accurate biochemical assignment of metabolites will improve our interpretation of HR-MAS data and the translation of NMR tumor biomarkers to in vivo studies. 1D and 2D HR-MAS NMR experiments were used to determine metabolites of brain tumor (astrocytoma grade II, grade III gliomas, glioblastomas). We developed this project on gliomas with the aim to gain a better insight into the discrimination among different grades and subtypes using ex vivo HR-MAS NMR, in vivo MRS, MRI, clinical data and statistical analysis. We report experiments performed on 15 specimen already collected from different grade glioma. Different amount of some small metabolites such as alanine, lactate, glutamine, glutamate, myo-inositol and glycine in two different ex vivo high grade glioma samples. The ex vivo spectra obtained on samples from different locations, line-broadened in order to be compared with the in vivo MR spectrum, obtained from the same selected voxel. A number of metabolites have been identified as potential biomarkers of tumor type; now we need to combine all the in vivo, ex vivo, histological and clinical data to obtain a unique tumor fingerprints. Results gathered from this study should lead to the development of tools that can facilitate the distinction of tumor types and grade that cannot be readily distinguished by histopathology or by routine neuroimaging.

2012 - HR-MAS NMR of fruits of plants belonging to the Rutaceae family [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; V., Righi; Schenetti, Luisa
abstract

Citrus, as one of the worldwide favourite fruits, draws more attention recently due to its therapeutic potentials. In animal models, d-limonene and structural analogues have demonstrated strong chemopreventive effects in lymphomas, mammary, gastric, liver, and lung cancers. [P.L. Crowell, M.N. Gould, Crit. Rev. Oncog. 5, 1, 1994] Limonoids, citrus secondary metabolites, seem to have multiple bioactive functions, including anticancer, reducing cholesterol, anti-anxiety, antimicrobial, and antiviral activities. [G. D. Manners, J. Agric. Food Chem. 2007, 55, 8285.] This is a HR-MAS NMR study on samples from exocarp, mesocarp, endocarp and seeds of Citrus Medica and Citrus Limon fruits aimed at to the evaluation of the potentialities of the technique in the detection and identification of terpenes in different parts of the fruit.1D (water-presaturated, spin-echo and diffusion-filtered spectra) as well as 2D NMR experiments (COSY, TOCSY and HSQC) are carried out at 4 °C on different regions of the commercial fruit cut in pieces that can fit the HR-MAS 4 mm rotor and directly put into it. Attempts at gaining some insight into the dimensions of oil bodies in the flavedo through diffusion experiments will be also presented.

2012 - Low Bandgap Copolymers with (Alkylsulfanyl) Bithiophene Unit for Efficient Polymer Solar Cells [Relazione in Atti di Convegno]
P., Morvillo; Parenti, Francesca; R., Diana; E., Bobeico; Mucci, Adele; Tassinari, Francesco; Schenetti, Luisa; C., Minarini
abstract

Polymer solar cells have evolved as a promising cost-effective alternative to silicon-based ones. However, low efficiency of these plastic devices limits their feasibility for commercial use. The efficiencies of polymer photovoltaic cells got a major boost with the introduction of the bulk heterojunction (BHJ) configuration consisting of an interpenetrating network of electron donor and acceptor materials. Recently, benzodithiophene based polymers has been used as electron donors in polymer solar cells showing very promising properties such as an increasing charge transport and a red shift of the absorption spectra. In this work the synthesis, the spectroscopic and photovoltaic characterization of a copolymer based on (octylsulfanyl)bithiophene and benzo[1,2-b:4,5-b’]dithiophene units and a polymer based on (butylsulfanyl)bithiophene unit are reported. BHJ solar cells using these polymers as donor materials blended with [70]PCBM as acceptor were prepared and investigated. The geometry of the device is: glass/ITO/PEDOT:PSS/blend/Ca/Al. The electrical performances of the cells were compared in order to study the influence of the benzodithiophene unit on the polymer backbone. The power conversion efficiency of the best realized polymer solar cell is 2.3% under 100 mW/cm2 AM 1.5G illumination

2012 - Low band gap thienothiophene-thiophene copolymer: synthesis, characterization and application in polymer solar cells [Abstract in Atti di Convegno]
P., Morvillo; Parenti, Francesca; R., Diana; Fontanesi, Claudio; M., Lanzi; Mucci, Adele; Tassinari, Francesco; Schenetti, Luisa
abstract

Polymer solar cells (PSCs) have recently attracted considerable attention due to their advantages of low cost, light weight, processability and compatibility with large scale flexible substrates. The most efficient device architecture of polymer solar cells is based on the bulk heterojunction concept in which the active layer, sandwiched between two electrodes with different work functions, consists of a blend of electron donating material, e.g. a p-type conjugated polymer, and an electron accepting material (n-type), such as fullerene derivatives.Polythiophenes are quite interesting materials for this purpose, combining the above described advantages with an enhanced photochemical stability, compared with poly(p-phenylene vinylene) and poly p-phenylene. In this work the synthesis, the spectroscopic and photovoltaic characterization of a thienothiophene-thiophene copolymer are reported. Poly[2-nonanoylthieno[3,4-b]thiophene-4,6-diyl-alt-4,4’-bis(octylsulfanyl)-2,2’-bithiophene]) was obtained by Stille coupling between the dibromo derivative of 2-nonanoylthienothiophene and a distannyl derivative of bis(octylsulfanyl)bithiophene.Bulk heterojunction solar cells using these polymers as donor materials blended with PCBM as acceptor were prepared and investigated. The geometry of the device is: glass/ITO/PEDOT:PSS/Polymer:PCBM/Ca/Al. An efficient charge transfer between the donor and PCBM takes place and the best device obtained has and efficiency of 1% under simulated light (AM1.5G). Further improvement of the efficiency using different acceptors, optimizing layer thickness and lowering polymer impurities can be envisaged.

2012 - MRS study of meningeal hemangiopericytoma and edema: A comparison with meningothelial meningioma [Articolo su rivista]
Righi, V.; Tugnoli, V.; Mucci, Adele; Bacci, A.; Bonora, S.; Schenetti, Luisa
abstract

Intracranial hemangiopericytomas (HPCs) are rare tumors and their radiological appearance resembles that of meningiomas, especially meningothelial meningiomas. To increase the knowledge on the biochemical composition of this type of tumor for better diagnosis and prognosis, we performed a molecular study using ex vivo high resolution magic angle spinning (HR-MAS) magnetic resonance spectroscopy (MRS) perfomed on HPC and peritumoral edematous tissues. Moreover, to help in the discrimination between HPC and meningothelial meningioma we compared the ex vivo HR-MAS spectra of samples from one patient with HPC and 5 patients affected by meningothelial meningioma. Magnetic resonance imaging (MRI), in vivo localized single voxel 1H-MRS was also performed on the same patients prior to surgery and the in vivo and ex vivo MRS spectra were compared. We observed the presence of OH-butyrate, together with glucose in HPC and a low amount of N-acetylaspartate in the edema, that may reflect neuronal alteration responsible for associated epilepsy. Many differences between HPC and meningothelial meningioma were identified. The relative ratios of myo-inositol, glucose and gluthatione with respect to glutamate are higher in HPC compared to meningioma; whereas the relative ratios of creatine, glutamine, alanine, glycine and choline-containing compounds with respect to glutamate are lower in HPC compared to meningioma. These data will be useful to improve the interpretation of in vivo MRS spectra resulting in a more accurate diagnosis of these rare tumors.

2011 - (Alkylsulfanyl)bithiophene-alt-Fluorene: π-Conjugated Polymers for Organic Solar Cells [Articolo su rivista]
Parenti, Francesca; Pasquale, Morvillo; Eugenia, Bobeico; Rosita, Diana; Massimiliano, Lanzi; Fontanesi, Claudio; Tassinari, Francesco; Schenetti, Luisa; Mucci, Adele
abstract

We describe the synthesis of alternating bithiophene–fluorenecopolymers (P1–P3) with different regiochemistry of thebithienyl unit and different alkylsulfanyl chain lengths. Thestructural, electrochemical and photophysical properties ofthese polymers were investigated by gel permeationchromatography (GPC), differential scanning calorimetry(DSC), NMR, UV/Vis and photoluminescence (PL) spectroscopyand cyclic voltammetry (CV), and the polymerswere used to assemble organic solar cells (OSCs), in combi-IntroductionOrganic conjugated materials are attracting increased attentiondue to their potential in the fields of chemical sensors,[1] electroluminescent devices,[1c,2] field-effect transistors[3] and OSCs.[4] The last is one of the most appealingapplications of conjugated polymers because they have thepotential to be a low cost alternative to conventional inorganicsemiconductors.[5] The major desirable features ofOSCs are mechanical flexibility, very high speed of processingand low cost for large area fabrication.[6] The mostefficient device architecture of polymeric solar cells is basedon the bulk heterojunction concept (BHJ),[7] in which theactive layer, sandwiched between two electrodes with differentwork functions, consists of a blend of electron donatingmaterial, e.g. a p-type conjugated polymer, and an electronaccepting material (n-type), such as fullerene derivatives.For application in OSCs, conjugated polymers should[a] Dipartimento di Chimica, Università di Modena e ReggioEmilia,Via G. Campi 183, 41125 Modena, ItalyFax: +39-059373543E-mail: adele.mucci@unimore.it[b] ENEA, C.R. Portici,Piazzale E. Fermi 1, 80055 Portici (NA), ItalyE-mail: pasquale.morvillo@enea.it[c] Dipartimento di Chimica Industriale e dei Materiali, Universitàdi Bologna,V.le del Risorgimento 4, 40136 Bologna, ItalySupporting information for this article is available on theWWW under http://dx.doi.org/10.1002/ejoc.201100738.Eur. J. Org. Chem. 0000, 0–0 © 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1nation with the fullerene derivative methyl [6,6]-phenyl-C61-butyrate (PCBM). P3, with a head-to-head bithienyl unit,shows a broader absorption and a lower band gap with respectto P1 and P2, which have tail-to-tail bithienyl units.The PL intensity of P1–P3 is dramatically quenched in thepresence of PCBM, demonstrating that an efficient chargetransfer between donor and acceptor occurs. The best OSCdevice was obtained with P3.

2011 - EPA or DHA Supplementation Increases Triacylglycerol, but not Phospholipid, Levels in Isolated Rat Cardiomyocytes [Articolo su rivista]
V., Righi; M., Di Nunzio; F., Danesi; Schenetti, Luisa; Mucci, Adele; E., Boschetti; P., Biagi; S., Bonora; V., Tugnoli; A., Bordoni
abstract

It is well recognized that a high dietary intakeof long-chain polyunsaturated fatty acids (LC-PUFA) has profound benefits on health and prevention of chronic diseases. In particular, in recent years there has beena dramatic surge of interest in the health effects of n-3LC-PUFA derived from fish, eicosapentaenoic (EPA) anddocosahexaenoic (DHA) acids. Notwithstanding, the metabolicfate and the effects of these fatty acids once insidethe cell has seldom been comprehensively investigated.Using cultured neonatal rat cardiomyocytes as model systemwe have investigated for the first time, by means ofhigh-resolution magic-angle spinning nuclear magneticresonance (HR-MAS NMR) spectroscopy in combination with gas chromatography (GC), the modification occurringin the cell lipid environment after EPA and DHA supplementation.The most important difference between controland n-3 LC-PUFA-supplemented cardiomyocytes highlightedby HR-MAS NMR spectroscopy is the increase ofsignals from mobile lipids, identified as triacylglycerols(TAG). The observed increase of mobile TAG is a metabolicresponse to n-3 LC-PUFA supplementation, whichleads to an increased lipid storage. The sequestration ofmobile lipids in lipid bodies provides a deposit of storedenergy that can be accessed in a regulated fashion according to metabolic need. Interestingly, while n-3LC-PUFA supplementation to neonatal rat cardiomyocytes causes a huge variation in the cell lipid environment, itdoes not induce detectable modifications in water-soluble metabolites, suggesting negligible interference with normal metabolic processes

2011 - HR-MAS NMR SPECTROSCOPY FOR CHARACTERIZATION OF STEATOSIC LIVER: FAT QUANTIFICATION FOR A SPECTROSCOPIC DIFFERENTIATION BETWEEN STEATOSIS AND STEATOHEPATITIS [Abstract in Atti di Convegno]
Righi, Valeria; Stentarelli, Chiara; Guaraldi, Giovanni; Zona, Stefano; Ligabue, Guido; Besutti, Giulia; Loria, Paola; Luisa, Losi; Luca, Nocetti; Vitaliano, Tugnoli; Schenetti, Luisa; Mucci, Adele
abstract

Non-alcoholic fatty liver disease (NAFLD) is a common cause of chronic liver disease. The NAFLD includes non-alcoholic fatty liver (NAFL) and non-alcoholic steatohepatitis (NASH) [1]. The mechanisms of NAFL to NASH transition remain to be clarified [2]. NAFLD appears to originate from the dysregulation of hepatic lipid metabolism as a part of the metabolic syndrome accompanied by visceral obesity, dyslipidemia, atherosclerosis and insulin resistance. A recent study has also demonstrate that high prevalence of steatosis is correlated to HCV-related chronic hepatitis [3]. High Resolution Magic Angle Spinning (HR-MAS) NMR is a useful tool for the metabolic characterization of intact tissues [4] and can be used to support the clinical diagnosis. The first aim of this study is to characterize the NAFL and NASH metabolism using HR-MAS NMR Spectroscopy. The second one is to evaluate the possible transition from NAFLD to NASH quantifying the liver fat content (LFC), both in ex-vivo and in-vivo NMR Spectroscopy. Patients with indication for steatosis underwent in-vivo 1H MR Spectroscopy analysis and liver biopsy. Histopathological analysis provided steatosis percentage, steatosis grade and fibrosis. A fragment of biopsy specimen was used for HR-MAS analysis, to obtain metabolic tissue characterization. Univariate linear regression analysis and Pearson r coefficient were used to study the relationship between histological steatosis percentage and LFC, estimated through HR-MAS analysis and in-vivo Spectroscopy. Similar high associations were found between LFC estimated by HR-MAS and histological steatosis percentage (r=0,71; p=0,006) and between LFC estimated by in-vivo Spectroscopy and histological steatosis percentage (r=0,79; p=0,002). HR-MAS spectra showed a high tissue metabolic heterogeneity, with particular regard to the content of free glucose, alanine, glutamine/glutamate and phospholipids. Fibrotic liver showed a higher presence of small metabolites such as choline. HR-MAS NMR Spectroscopy, well estimates the fatty infiltration of the liver. Future research on HR-MAS spectral heterogeneity may allow to find biochemical metabolic indicators of steatosis progression to be used in the differentiation between steatohepatitis and steatosis through in-vivo MR Spectroscopy.[1] Contos M. J. and Sanyal A. J., The clinicopathologic spectrum an management of nonalcoholic fatty liver disease. Adv Anat Pathol, 9, 37-51 (2002).[2] Reid A. E., Nonalcoholic steatohepatitis . Gastroenterol, 121, 710-23 (2001).[3] Scheuer P. J., Ashrafzaddeh P., Sherlock S., Brown D., Disheiko G. M., the pathology of hepatitis C. Hepatology, 25, 567-71. (1992).[4] Righi V., Durante C., Cocchi M., Calabrese C., Di Febo G., Lecce F., Pisi A., Tugnoli V., Mucci A. and Schenetti L., Discrimination of healthy and neoplastic human colon tissues by ex vivo HR-MAS NMR spectroscopy and chemometric analyses. J of Proteome Res, 8, 1859-69 (2009).

2011 - Multiecho MR sequences and high-resolution magic angle spinning (HRMAS)ex-vivo spectroscopy in the qualitative analysis and differentiationbetween steatohepatitis and steatosis [Abstract in Rivista]
Besutti, Giulia; Ligabue, Guido; L., Nocetti; F., Fiocchi; Stentarelli, Chiara; Mucci, Adele; Loria, Paola; Guaraldi, Giovanni; Torricelli, Pietro
abstract

Purpose: To compare multiecho gradient-echo MR (magnetic resonance) sequencesin the differentiation between steatohepatitis and steatosis and to describeHR-MAS spectra of liver biopsy showing steatohepatitis or steatosis.Methods and Materials: Fourteen patients with indication for biopsy assessmentof steatosis underwent liver biopsy (reference standard) and MR imaging. Liverbiopsy of both viral and metabolic steatosis were classified using NAFLD activityscore (NAS) which depicts the degree of necro-inflammatrory activity allowing todifferentiate between steatohepatitis and steatosis. Besides liver fat content (LFC),multiecho sequences were also used to calculate water and fat relaxation times(T2*), which are influenced by microenvironmental characteristics, so potentiallyassociated with necro-inflammatory activity. Relation between each multiechoparameter (LFC/T2*water/T2*fat) and NAS was estimated using univariate linearregression and Pearson coefficient. A fragment of biopsy specimen was analysedthrough HR-MAS to obtain metabolic tissue characterisation.Results: Association was found between: NAS and LFCmulti (r = 0.7; p = 0.006),NAS and T2*fat (r = -0.73, p = 0.063, ns, T2*fat was available for 7 patients only).No correlation was found between NAS and T2*water. HR-MAS spectra showedtissue metabolic heterogeneity, with particular regard to the contents of free glucose,alanine, glutamine/glutamate and phospholipids.Conclusion: This pilot study describes multiecho parameters associated withhistological necro-inflammatory activity, allowing to study the potential capability ofMR to differentiate between steatohepatitis and steatosis. Description of HR-MASspectral heterogeneity in NAFLD and NASH may allow to find biochemical indicatorsof steatosis progression to be used in differentiating between steatohepatitisand steatosis in spectra acquired with in vivo MR Spectroscopy too.

2011 - Organic Materials for Phovoltaics: Synthesis and Electrochemical Behaviour of a Thiophene Based Copolymer [Abstract in Atti di Convegno]
Parenti, Francesca; R., Diana; Fontanesi, Claudio; P., Morvillo; Mucci, Adele; Schenetti, Luisa; Tassinari, Francesco
abstract

Polymer solar cells (PSCs) have recently attracted considerable attention due to their advantages of low cost, light weight, processability and compatibility with large scale flexible substrates [1]. Polythiophenes are quite interesting materials for this purpose, combining the above described advantages with an enhanced photochemical stability, compared with poly(p-phenylene vinylene) and poly p-phenylene.In this communication the synthesis, the spectroscopic, the electrochemical and photovoltaic characterization of a thiophene based copolymerare reported. The synthesis was performed in analogy to ref. [2] via Stille coupling of a brominated and a stannilated comonomer as illustrated in Fig.1. The copolymer was characterised through 1H and 13C NMR, Uv-Vis spectroscopy, Cyclic Voltammetry.References[1] S. Gunes, H. Neugebauer, N. S. Sariciftci, “Conjugated Polymer-Based Organic Solar Cells” Chem. Rev. 107, 1324 (2007) ; M. Helgesen, R. Søndergaard, F. C. Krebs, “Advanced materials and processes for polymer solar cell devices”, J. Mater. Chem. 20, 36 (2010) ; J. Peet, J. Y. Kim, N. E. Coates, W. L. Ma, D. Moses, A. J. Heeger, G. C. Bazan, “Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols”, Nat. Mater. 6, 497 (2007) ; S. A. Gevorgyan and F. C. Krebs in Handbook of thiophene-Based materials, I. F. Perepichka and D. F. Perepichka ed. (John Wiley and Sons Ltd., 2009). [2]Yongye Liang, Danqin Feng, Yue Wu, Szu-Ting Tsai, Gang Li, Claire Ray and Luping Yu, “Highly Efficient Solar Cell Polymers Developed via Fine-Tuning of Structural and Electronic Properties”, JACS 131, 7792-7799 (2009)

2011 - Preparation and characterization of bithiophene modified Si(1,1,1) electrodes [Abstract in Atti di Convegno]
Tassinari, Francesco; Fontanesi, Claudio; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

The purpose of this work is to prepare a substituted oligothiophene (OT) modified electrode, in which the oligomer is capable of acting as a conductive wire between the electrode surface and the solution bulk.A simple model system is represented by a bithiophene chemically grafted to the surface of a hydrogen terminated n-doped Si(111) electrode. The possibility to functionalize with different moieties the lateral chain and the thiophene rings makes these systems very versatile and easily customizable.

2011 - Structural investigation and intracellular trafficking of a novel multicomposite cationic solid lipid nanoparticle platform as a pDNA carrier [Articolo su rivista]
Vighi, Eleonora; Leo, Eliana Grazia; Montanari, Monica; Mucci, Adele; Hanuskova, Miriam; Iannuccelli, Valentina
abstract

Background: The ability to efficiently cross cellular barriers and accomplish high-level transgene expression is a critical challenge to broad application of nonviral vectors, such as cationic solid lipid nanoparticles (SLN).Aims: This study aims to design and characterize in vitro multicomposite SLN as a novel platform for pDNA delivery.Results/Discussion: The distribution of each component (stearic acid, stearylamine, phosphatidylcholine, cholesterol, protamine and Pluronic F68) in the SLN matrix was studied by electron spectroscopy for chemical analysis and NMR in order to establish its influence on SLN cytotoxicity and transfection efficiency. Multicomposite SLN mediated the expression of enhanced green fluorescent protein in a way comparable with the positive control,but inducing a lower cytotoxicity. Moreover, the carrier exhibited the ability to enter the nucleoli, probably as a result of the synergic action of the nuclear localization signal of protamine and the flexibility of the lipid matrix owing to the phosphatidylcholine. Conclusion: The multicomposite SLN showed good transfection efficiency and negligible cytotoxicity, both crucial factors for an efficient gene-delivery system. Considering the fact that nucleolihave emerged in recent years as important targets in many fields, this novel carrier could have significant future therapy involvements whenever there is a requirement to overcome subcellular barriers. However, further work needs to be carried out in order to fully characterize the formulation, to elucidate where alternative colloidal structures might exist and play a role in obtaining the results presented.

2010 - Cidofovir-loaded liposomes: an intro-study using BCBL-1 cell line as a model for primary effusion lymphoma [Articolo su rivista]
Ruozi, Barbara; Riva, Giovanni; Belletti, Daniela; Tosi, Giovanni; Forni, Flavio; Mucci, Adele; Barozzi, Patrizia; Luppi, Mario; Vandelli, Maria Angela
abstract

Cidofovir (HPMPC) was recently reported to exert a valuable antineoplastic activity against primary effusion lymphoma (PEL), a B-cell neoplasm associated with Human Herpesvirus-8 (HHV-8) infection. In this study, we developed and characterized liposomes encapsulating HPMPC to increase drug efficacy reducing the administered dose and the related toxicity, which actually hamper its clinical therapeutic use in patients affected with PEL. The liposomes, obtained using different formulations of neutral and cationic lipids, were analyzed by microscopical (AFM) and spectroscopical (PCS and NMR) techniques. Using an in vitro model of PEL (BCBL-1 cell line), the carrier toxicity and the antineoplastic efficacy of liposomes were evaluated by flow cytometry applying apoptosis and cell death analysis. The in vitro study showed the applicability of the liposomes within a restricted range of lipidic concentrations according to the lipids used during the preparation. The moderate increases in the percentage of apoptotic/necrotic cells suggests that liposomal delivery allows the release of HPMPC into BCBL-1 cells enabling an unexpectedantineoplastic activity of this drug even at lower doses.

2010 - Detecting the transition from normal to malignant phenotype in the brain of rats bearing implanted C6 gliomas by multinuclear HR MAS and genomic analysis [Abstract in Atti di Convegno]
Righi, Valeria; P., Lopez Larrubia; Schenetti, Luisa; Mucci, Adele; V., Tugnoli; M. L., García Martín; S., Cerdán
abstract

We report a 1H and 13C HR-MAS NMR study of normal and diseased brain regions of rats bearing C6 gliomas implanted. The detection of selectively enriched metabolites through ex vivo HR-MAS spectroscopy and the correlations with the expression of the genes involved in the glycolytic metabolism are the aims of this work. C6 gliomas wereinduced in rats and tumour growth was evaluated in vivo using T1 andT2 weighted MRI. Three weeks after C6 implantation, rats wereinfused with [1-13C] glucose and then cerebral metabolism wasarrested. The fixed brain was removed from the skull and five biopsieswere taken from different brain regions. The 1H spectra show theincrease in Lac and mobile lipids in the tumour biopsies and the 13C spectra present a significant increase of (3-13C) Lac and decrease of (4-13C) Glu and (4-13C) Gln, revealing a marked increase in glycolytic metabolism in the tumour. Then, we investigated the individual expression of specific genes coding for enzymes involved in the glycolytic pathway, to improve our understanding of the genetic basis of the metabolic profile observed by 13C HR-MAS.

2010 - Experimental and Theoretical Study of the p- and n-Doped States of Alkylsulfanyl Octithiophenes [Articolo su rivista]
C., Bruno; F., Paolucci; M., Marcaccio; Benassi, Rois; Fontanesi, Claudio; Mucci, Adele; Parenti, Francesca; L., Preti; Schenetti, Luisa; Vanossi, Davide
abstract

The charge-transfer and spectral properties of two octithiophenes, namely 4′,4′′′,3′v,3v′-tetra(octylsulfanyl)-2,2′:5′,2′′:5′′,2′′′:5′′′,2′v:5′v,2v:5v,2v′:5v′,2v′′-octithiophene and 4,3′′,4v,4v′′-tetrabromo-4′,4′′′,3′v,3v′-tetra[(R)-2-methylbutylsulfanyl]-2,2′:5′,2′′:5′′,2′′′:5′′′,2′v:5′v,2v:5v,2v′:5v′,2v′′-octithiophene, OT1 and OT2, respectively,are characterized by cyclic voltammetry and spectroelectrochemistry under ultradry conditions. The analysisof the voltammetric results shows the formation of up to the dication for both OT1 and OT2 and up to thetetraanion (OT1) and trianion (OT2) anions. The optical properties of the OT1 (2+, 1+, neutral, 1-, 2-)species were probed by in situ UV-vis-NIR spectroelectrochemistry. The calculated standard potentials atthe B3LYP/cc-pVTZ level of the theory allowed the rationalization of the experimental electrochemical results.The UV-vis-NIR spectra were successfully compared with the theoretical electronic transitions and oscillatorstrength data obtained by time-dependent B3LYP/6-31G* calculations. Theoretical redox potentials and opticaltransitions properties are calculated including “the solvent effect” within the CPCM model. The consistencyobtained between experimental and theoretical results indicates the existence of the hypothesized high-spin/high-charge p- and n-doped electronic states for the OT1 and OT2 octithiophenes here studied.

2010 - Interaction studies of a β-cysteine functionalized polythiophene with biomolecules [Abstract in Atti di Convegno]
Bortolotti, Carlo Augusto; F., Filace; Parenti, Francesca; Mucci, Adele; Schenetti, Luisa
abstract

Polythiophenes are an important representative class of conjugated and thermally stable polymers that can be used in alternative to inorganic semiconductors in optical and electronic devices [1]. Recently, they have been studied as biological sensors [2], thanks to the presence of the electroconducting backbone together with β-substituents able to interact with biological species. The interaction between the polymer side chain functionalities and the analyte can be of different type (hydrogen bonds, ionic interactions …) depending on the analyte, or the backbone itself can directly interact with the biomolecule through π-π stacking.In this study, a previously synthesized β-cysteine functionalized polythiophene (PTCys, Fig 1) [3] was investigated as folic acid [4] and cytochrome C (horse heart) biosensor.[1] Skotheim Ed. T., Reynolds J., Elsenbamer R., Dekker Marcel, Inc., New York, NY, USA, Handbook of conducting polymers 2nd Edition, 1998; Skotheim Ed. T., Dekker Marcel, Inc., New York, NY, USA, Handbook of conducting polymers 1986[2] Berggren, M.; Inganas, O.; Gustafsson, G.; Nature,1994, 372, 444-446[3] Cagnoli R., Lanzi M., Mucci A., Parenti F., Schenetti L., Polymer, 2005, 46(11), 3588-3596[4] Zhiyi Yao, Chun Li and Gaoquan Shi, Langmuir,2008, 24, 12829-12835

2010 - MR techniques in the qualitative analysis of liver steatosis: the potential in the differentiation between steatohepatatis and steatosis [Abstract in Rivista]
Besutti, Giulia; L., Nocetti; Stentarelli, Chiara; Zona, Stefano; Scaglioni, Riccardo; Loria, Paola; S., Ballestri; V., Righi; Mucci, Adele; L., Losi; Torricelli, Pietro; Guaraldi, Giovanni; Ligabue, Guido
abstract

To evaluate multiecho MR techniques in the differentiation between steatohepatitis and steatosis, using liver biopsy as the reference standard, in patients with and without HIV infection.

2010 - Metabolic aspects of n-3 PUFAs supplementation to rat cardiomyocytes: a HR-MAS NMR and GC/MS study [Relazione in Atti di Convegno]
Righi, Valeria; M., Di Nunzio; F., Danesi; E., Boschetti; Schenetti, Luisa; Mucci, Adele; A., Bordoni; V., Tugnoli
abstract

Cardiovascular diseases (CVD) are responsible for significant morbidity and mortality throughout the world. We present a first investigation using HR-MAS NMR Spectroscopy in combination with GC/MS of neonatal rat cardiomyocytes supplemented with two different PUFAs, EPA and DHA, in order to understand the metabolic change occurring in these cells following the increase of their n-3 PUFA content. EPA and DHA are of special importance for human health, and fish oil feeding has beenassociated to reduced mortality in several studies.

2010 - MyMRs: Map your Magnetic Resonance stuff! [Abstract in Atti di Convegno]
M. A., Cremonini; S., Davalli; R., Gobetto; A., Macchioni; Mucci, Adele; M., Valentini
abstract

Due to the widespread diffusion of magnetic resonance (MR) equipment, it is sometimes difficult to keep track of all the magnetic resonance instrumentation available in a country. Paradoxically, while a high number of recent and less recent instruments may be present in a country area, they are often unknown to the occasional user (and sometimes even to some specialists), because of lack of communication within the scientific community. The problem may be exacerbated by thewell known “bad practics” of letting information spread only within groups of “homogeneous” scientists, so that – so to speak – chemists talk only to chemists, physicists to physicists and so on.As a step toward the solution of this problem, the GIRM (the Interdivisional Group of Magnetic Resonance of the Italian Chemical Society) has begun a project called MyMRs (http://www.soc.chim.it/gruppi/girm/mymrs), based on the well known Google maps, by which the MR instruments are graphically displayed as placeholders with different colors (yellow = NMR spectrometer,red = relaxometer, green = EPR spectrometer, blue = MRI equipment). All relevant information is obtained from the MR community through a form connected to a spreadsheet via the “Google docs” web site, converted to KML format with a simple BASH script and eventually shown in a baloon when a placeholder is clicked. The authors – who are member of the GIRM board – thank all Italian and foreign collegues who will want to provide data about their MR equipment.

2010 - Non-alcoholic Fatty Liver Disease: a HR-MAS analysis [Abstract in Atti di Convegno]
F., Filace; Righi, Valeria; Stentarelli, Chiara; Guaraldi, Giovanni; V., Borghi; Zona, Stefano; Ligabue, Guido; G., Busetti; Loria, Paola; Ballestri, Stefano; L., Losi; L., Nocetti; Schenetti, Luisa; Mucci, Adele
abstract

Non-alcoholic fatty liver disease (NAFLD) is a common cause of chronicliver disease. The NAFLD includes non-alcoholic fatty liver (NAFL) andnon-alcoholic steatohepatitis (NASH). The mechanisms of NAFLD to NASH transition remain to be clarified. NAFLD appears to originate from the dysregulation of hepatic lipid metabolism as a part of the metabolicsyndrome accompanied by visceral obesity dyslipidemia, atherosclerosis, and insulin resistance. High Resolution Magic Angle Spinning (HR-MAS) NMR is a useful tool for the metabolic characterization of intact tissues and can be used to support the clinical diagnosis. The aim of this study is to characterized the NAFLD and NASH metabolism using HR-MAS NMR Spectroscopy, and to evaluate the possible transition from NAFLD to NASH. Liver needle biopsies were collected for the HR-MAS and histological analyses. Preliminary HR-MAS NMR results show a higher amount of lipids in the biopsies from patients with 30-50% of steatosis, whereas lipids and of small metabolites are present when the liver is affected from a market fibrosis.

2010 - Octithiophenes via One-Pot Oxidative Coupling of 4-(ω-Functionalized Alkylsulfanyl)-2,2′-Bithiophenes [Articolo su rivista]
L., Preti; R., Cagnoli; Parenti, Francesca; M., Lanzi; Libertini, Emanuela; Pinetti, Diego; Schenetti, Luisa; Mucci, Adele
abstract

The oxidative coupling reaction with FeCl3 on nitrile, methyl ester and amino functionalized 4-(alkylsulfanyl)-2,2’-bitiophenes afforded symmetric octithiophenes (OTs). These new OTs have solvatochromic properties similar to those reported for poly(ω-functionalized alkylsulfanyl)thiophenes and have a potential use in optoelectronic devices. The carboxy (obtained through hydrolysis from nitrile and methyl ester functionalized OTs) and the amino functionalized OTs are also water soluble as salts. From this and our previous results, the oxidative coupling with FeCl3 can be proposed as a general method for the synthesis of OTs when the starting materials are 4-(alkylsulfanyl)-, 4-(ω-functionalized alkylsulfanyl)-, and 4-alkylsulfanyl-4’-halo-2,2’-bithiophenes.

2010 - Study of the metal complexation-ability of Nitrile functionalised oligo and polythiophenes: synthesis and study of the metal complexation-ability [Abstract in Atti di Convegno]
Parenti, Francesca; Fontanesi, Claudio; Schenetti, Luisa; Mucci, Adele
abstract

The synthesis and the complexation properties of some β-sulfanylheptanenitrile functionalised oligo- and polythiophenes reported are studied. The ability of these polymers towards the complexation of different transition metals is compared, in order to get insight into the influence of the substitution density and of the conjugation length on the chelating skills. The complexation-ability is a crucial property in view of possible applications of these materials as chemical sensors for metal ions detection1 or as carbon substitute materials for catalyst support for oxygen reduction or methanol oxidation in direct methanol fuel cells2 (DMFC).References:1) J. Maiti, B. Pokhrel, R. Boruah, S.K.Dolui, Sensors and Actuators B: Chemical 2009, 141,447-451; A.Pietrangelo, M. N. Roberts, M. J. MacLachlan, M.O.Wolf, Polymer Preprints 2009, 50, 280.2) M. Saito, H. Shiroishi, C.to Onoa, S. Tsuzuki, T. Okadaa, Y. Uchimoto, Journal of Molecular Catalysis A: Chemical 2006, 248, 99–108; R. P. Kingsborough, T. M. Swager, Chemistry of Materials 2000, 12, 872-874.

2009 - 1H HR-MAS and genomic analysis of human tumor biopsies discriminates between high and low grade astrocytomas [Articolo su rivista]
V., Righi; J. M., Roda; J., Paz; Mucci, Adele; V., Tugnoli; G., Rodriguez Tarduchy; L., Barrios; Schenetti, Luisa; S., Cerdán; M. L., García Martín
abstract

We investigate the profile of choline metabolites and the expression of the genes of the Kennedy pathway in biopsies ofhuman gliomas (n¼23) using 1H High Resolution Magic Angle Spinning (HR-MAS, 11.7 Tesla, 277 K, 4000Hz) and individual genetic assays. 1H HR-MAS spectra allowed the resolution and relative quantification by the LCModel of the resonances fromcholine (Cho),phosphocholine (PC) and glycerophosphorylcholine (GPC), the three main components ofthe combined tCho peak observed in gliomas by in vivo 1H NMR spectroscopy. All glioma biopsies depicted a prominenttChopeak. However, the relative contributions ofCho, PC, andGPC totChowere different for lowandhighgrade gliomas.Whereas GPC is the main component in low grade gliomas, the high grade gliomas show a dominant contribution of PC.This circumstance allowed the discrimination of high and low grade gliomas by 1H HR-MAS, a result that could not be obtained using the tCho/Cr ratio commonly usedby in vivo 1HNMR spectroscopy. The expression of the genes involved in choline metabolismhas been investigated in the same biopsies. High grade gliomasdepict an upregulation of the beta gene of choline kinase and phospholipase C, aswell as a downregulation of the cytidyltransferase B gene, the balance of these being consistent with the accumulation of PC. In the low grade gliomas, phospholipase A1 and lysophospholypase are upregulated and phospholipase D is downregulated, supporting the accumulation of GPC. The present findings offer a promising procedure thatwill potentially helptoaccuratelygrade gliomatumors using1HHR-MAS, providinginaddition the genetic background for the alterations of choline metabolism observed in high and low grade gliomas.

2009 - AFM phase imaging of soft-hydrated samples: A versatile tool to complete the chemical-physical study of liposomes [Articolo su rivista]
Ruozi, Barbara; Tosi, Giovanni; Tonelli, Massimo; Bondioli, Lucia; Mucci, Adele; Forni, Flavio; Vandelli, Maria Angela
abstract

Despite of the several approaches applied to the physicochemical characterization of liposomes, few techniques are really useful to obtain information about the surface properties of these colloidal drug-delivery systems. In this paper, we demonstrate a possible new application of tapping mode atomic force microscopy (AFM) to discriminate between conventional and pegylated liposomes. We showed that the differences on liposomal surface properties revealed by the phase images AFM approach well correlate with the data obtained using classical methods, such as light scattering, hydrodynamic, and nuclear magnetic resonance analysis.

2009 - Discrimination of Healthy and Neoplastic Human Colon Tissues by ex Vivo HR-MAS NMR Spectroscopy and Chemometric Analyses [Articolo su rivista]
V., Righi; Durante, Caterina; Cocchi, Marina; C., Calabrese; G., Di Febo; F., Lecce; A., Pisi; V., Tugnoli; Mucci, Adele; Schenetti, Luisa
abstract

The metabolic profile of human healthy and neoplastic colorectal tissues was obtained using ex vivo High-Resolution Magic Angle Spinning (HR-MAS) NMR spectroscopy. Principal Components Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA) were applied to NMR data in order to highlight the biochemical differences between healthy and neoplastic colorectal tissues. The synergic combination of ex vivo HR-MAS NMR spectroscopy with Multivariate Data Analysis enables discrimination between healthy and tumoral colorectal tissues and identification of the increase of taurine, acetate, lactate, and lipids, and the decrease of polyols and sugars as tumoral characteristics. Moreover, it was found that macroscopically/histologically normal colorectal tissues, collected at least 15 cm from the adenocarcinoma, are characterized by a metabolic pattern quite similar to that typical of tumoral lesions.It was shown that ex vivo HR-MAS NMR spectroscopy, performed on intact specimens, may be of great potentiality in the clinical evaluation of human neoplastic colorectal tissues and that thebiochemical data represent the molecular basis for an accurate and noninvasive clinical applications of in vivo NMR spectroscopy.

2009 - Electrostatic LbL construction and characterization of photoelectrochemical solar cells based on water soluble polythiophenes and carbon nanotubes [Relazione in Atti di Convegno]
V., Sgobba; A., Troeger; A., Mateo Alonso; M., Prato; Parenti, Francesca; Cagnoli, Rita; Mucci, Adele; Schenetti, Luisa; D. M., Guldi
abstract

Positively and negatively charged functionalized polythiophenes and single walled carbon nanotubes (SWNT) were sequentially adsorbed on indium tin oxide (ITO) electrodes by electrostatic and van der Waals interactions using the layer by layer (LbL) deposition method. Optical, microscopic and spectroelectrochemical properties of mono and multistacks of SWCNT and PT polyelectrolyte containing sulfonate (1) and ammonium (2) side groups, were investigated. Upon illumination, monochromatic incident photoconversion efficiencies of 8.2 and 4.3 % were determined for eight stacks of single walled carbon nanotubes with ammonium and sulphonate polythiophene derivatives, respectively.

2009 - Electrostatic layer-by-layer construction and characterization of photoelectrochemical solar cells based on water soluble polythiophenes and carbon nanotubes [Articolo su rivista]
V., Sgobba; A., Troeger; Cagnoli, Rita; A., Mateo Alonso; M., Prato; Parenti, Francesca; Mucci, Adele; Schenetti, Luisa; D. M., Guldi
abstract

Positively and negatively charged functionalized polythiophenes and single walled carbon nanotubes were sequentially adsorbed on indium tin oxide electrodes by electrostatic and van der Waalsinteractions using the layer-by-layer deposition method. The resulting donor/acceptor photoelectrodes were tested as photoelectrochemical cells. Upon illumination, monochromatic incident photoconversion efficiencies of 8.2 and 4.3% were determined for eight stacks of single walled carbon nanotubes with ammonium and sulfonate polythiophene derivatives, respectively.

2009 - Experimental and theoretical investigation of the p- and n-doped states of alkylsulfanyl octithiophenes [Abstract in Atti di Convegno]
Fontanesi, Claudio; C., Bruno; M., Marcaccio; F., Paolucci; Benassi, Rois; Bortolotti, Carlo Augusto; Mucci, Adele; Parenti, Francesca; Preti, Lisa; Schenetti, Luisa
abstract

Thiophene based materials, oligothiophenes as well, are promising candidates for technological applications, being a possible alternative to high-cost traditional materials for electronics such as silicon. Thus, in this work the charge-transfer properties oftwo structurally related (Si and S2 as sketched on the left) octithiophenes are studied by means of cyclic voltammetryr”(CV). Digital simulations of CV data ,I— , suggest the reversible formation of up to the dication, for both Si and S2, andup to the 4- (Si) and 3- (S2) anions. The ‘ ‘electronic structure of the Si species (2+, i+, neutral, 1-, 2-) is probed by UV/Vis-NIR “in-situ” spectroelectrochemistry. Experimental results are compared to standard potentials calculated at the B3LYP/cc-pVTZ level of the theory and to electronic transition energy and oscillator strength data reckoned by time dependent B3LYP/6 calculations. The consistency observed between experimental and theoretical results indicates the existence, as stable species, of the hypothesized high-spin/high-charge p- and n-doped electronic states.

2009 - Experimental and theoretical investigation of the p- and n-doped states of alkylsulfanyl octithiophenes [Abstract in Atti di Convegno]
Fontanesi, Claudio; C., Bruno; M., Marcaccio; F., Paolucci; Benassi, Rois; Bortolotti, Carlo Augusto; Mucci, Adele; Parenti, Francesca; Preti, Lisa; Schenetti, Luisa
abstract

We characterizad the charge-transfer properties of two octithiophenes by means of cylcic voltammetry, UV-Vis-NIR spectroelectrochemistry and DFT calculations.

2009 - Identification of mobile lipids in human cancer tissues by ex vivo diffusion edited HR-MAS MRS [Articolo su rivista]
Righi, Valeria; Mucci, Adele; Schenetti, Luisa; A., Bacci; R., Agati; M., Leonardi; R., Schiavina; G., Martorana; G., Liguori; C., Calabrese; E., Boschetti; S., Bonora; V., Tugnoli
abstract

Magnetic Resonance Spectroscopy visible mobilelipids are considered important markers in the diagnosis ofhuman cancer and are thought to be closely involved in variousaspects of tumour transformation, such as cell proliferation,necrosis, apoptosis, hypoxia and drug resistance. A methodallowing the straightforward identification of the lipid classescontributing to the mobile lipids in human malignant tissuesis highly advisable. Ex vivo High Resolution Magic AngleSpinning Magnetic Resonance Spectroscopy was done directlyon human cerebral, renal and colorectal malignant tissuespecimens. A diffusion edited sequence, based on stimulatedecho and bipolar gradient pulses, was used to characterizemolecules with low diffusion rates, arising from mobile lipidcomponents. Cholesterol, triglycerides and phosphatidylcholineare simultaneously detected and all contribute to the mobilelipid resonances present in malignant glioma and clear cellrenal carcinoma tissue specimens spectra. On the contrary,papillary cell renal carcinoma spectrum is predominated byphosphatidylcholine resonances and that of colorectal adenocarcinoma is characterized by signals arising from triglycerides. Ex vivo diffusion edited High Resolution Magic AngleSpinning Magnetic Resonance Spectroscopy, done on intacttissue, is a powerful analytical tool to obtain a simple andimmediate identification of mobile lipid components. This can offer a significant contribution to better understanding their involvement in cancer tissues. Furthermore, ex vivo high resolution spectroscopic measurements allow to improve the interpretation of in vivo Magnetic Resonance spectra, increasing its clinical potentiality.

2009 - In vitro 1H and 31P NMR spectroscopy as a tool for investigating muscle energy state in facioscapulohumeral muscolar dystrophy (FSHD) mouse model [Abstract in Atti di Convegno]
Mucci, Adele; Ghiaroni, Valeria; Muscatello, Umberto; Tupler, Rossella; Schenetti, Luisa
abstract

Facioscapulohumeral muscular dystrophy (FSHD) is a hereditary neuromuscular disorder characterized by progressive weakness and atrophy of the facial, shoulder, abdominal and pelvic girdle muscles. We proposed that its pathogenesis could be associated with the over-expression of genes mapped at chromosome 4q35, ANT1, FRG1 and FRG2. Consistently, transgenic mice over-expressing FRG1 develop a progressive muscular dystrophy characterized by symptoms similar to those of human disease and thus it can be considered a reliable mice model to study FSHD. FSHD mouse model shows reduced tolerance to exercise and muscle weakness which can be related to disorders of muscle energy mechanisms.To investigate this hypothesis we have applied 1H and 31P NMR spectroscopy to wild-type and dystrophic vastus muscle PCA extracts to evaluate the muscle energy parameters by measuring the concentration of the major energy metabolites (ATP, ADP, AMP, Pi, Cr and PCr)

2009 - Quantitative Magic Angle Spinning Detection of Deuteration in Small Biopsies of Rat Brain [Abstract in Atti di Convegno]
M. R., Fayos Carrio; V., Righi; Mucci, Adele; Schenetti, Luisa; S., Cerdán
abstract

2D H,D-COSY and D,C-correlation experiments obtained on biopsies of rat brain fed with deuterium oxide are presented

2008 - "Aminoalkylsulfanyl substituted polithiophene: an aggregation study" [Abstract in Atti di Convegno]
Parenti, Francesca; Cagnoli, Rita; Caselli, Monica; Libertini, Emanuela; Mucci, Adele; Pinetti, Diego; Ponterini, Glauco; L., Preti; Schenetti, Luisa
abstract

The aggregation properties of poly{trimethyl-[7-(3-thienylsulfanyl)heptyl]ammonium iodide-co-thiophene} (PTN+Me3) (Fig.1) were investigated through NMR, AFM, light scattering and fluorescence spectroscopy.

2008 - A new NMR technique: HR-MAS applied to animal and vegetable soft materials [Capitolo/Saggio]
V., Righi; Schenetti, Luisa; Mucci, Adele
abstract

Nuclear Magnetic Resonance (NMR) Spectroscopy is widely employed for the identification and structural characterization of organic compounds in solution and in the solid state. In this contribution we are going to show some recent applications of a new NMR technique, namely High Resolution-Magic Angle Spinning (HR-MAS), to soft materials, in particular to porcine and veal meat, and to citrus lemon. HR-MAS technique can be considered a hybrid technique between solid-state and classical solution-state NMR. Dedicated HR-MAS probes permit to perform one-dimensional and two-dimensional (1D and 2D) correlation experiments, analogue to those commonly applied in solution, on semisolid samples, and to detect signals from metabolites and macromolecules.

2008 - Aggregation Properties of Aminoalkylsulfanyl Polythiophenes [Abstract in Atti di Convegno]
Cagnoli, Rita; Libertini, Emanuela; Mucci, Adele; Parenti, Francesca; Pinetti, Diego; Preti, Lisa; Schenetti, Luisa
abstract

The aggregation properties of an aminoalkylsulfanyl polythiophenes cayying a tromethylammonium group were characterized through a combined AFM, DOSY NMR and DLS study.

2008 - Aminoalkylsulfanyl Substituted Polythiophene: an Aggregation Study [Relazione in Atti di Convegno]
Parenti, Francesca; Pinetti, Diego; Ponterini, Glauco; Preti, Lisa; Schenetti, Luisa; Cagnoli, Rita; Caselli, Monica; Libertini, Emanuela; Mucci, Adele
abstract

The aggregation behaviour of poly{trimethyl-[7-(3-thienylsulfanyl)heptyl]ammonium iodide-co-thiophene} (PTN+Me3) was investigated through NMR, atomic force microscopy (AFM), dynamic light scattering (DLS), UV-Vis and fluorescence spectroscopy. The interaction with sodium ursodesoxycholate (NaUDC) causes a marked enhancement of fluorescence emission.

2008 - Amminoalchilsulfanil Politiofeni: come modulare la solubilità variando la sostituzione amminica [Abstract in Atti di Convegno]
Preti, Lisa; Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

E' presentata la sintesi di politiofeni recanti, sulle catene alchilsulfaniliche laterali, com sostituenti gruppi NH2, NR2, NR3+ e NRBoc. La solubilità di questi polimeri è modulata dal sostituente.

2008 - Biochemical Alterations from Normal Mucosa to Gastric Cancer by Ex vivo Magnetic Resonance Spectroscopy [Articolo su rivista]
Calabrese, C.; Pisi, A.; Febo, G. Di; Liguori, G.; Filippini, G.; Cervellera, M.; Righi, V.; Lucchi, P.; Mucci, Adele; Schenetti, Luisa; Tonini, V.; Tosi, M. R.; Tugnoli, V.
abstract

Background and Aims: The metabolic profile andmorphologic aspects of normal and pathologic humangastric mucosa were studied. The aim of the presentresearchwas the application of ex vivo high-resolutionmagic angle spinning magnetic resonance spectroscopy(HR-MAS MRS) to the human gastric tissue to getinformation on the molecular steps involved in gastriccarcinogenesis and the identification of biochemicalmarkers useful for the development of in vivo MRSmethodologies to diagnose gastric pathologies inclinical situations.Methods: Twelve normal subjects, five withautoimmuneatrophic gastritis, five with Helicobacter pyloriinfection, and five with adenocarcinoma were examined.Ten biopsies were taken during endoscopy fromeachpatient. Specimens from carcinoma were alsoobtained during gastrectomy. Of the 10 biopsies, 4 wereused for histologic evaluation, 4 were fixed in glutaraldehydeand processed for transmission and scanningelectron microscopy, and 2 were immersed in liquidnitrogen and stored at 85C for monodimensional andbidimensional ex vivo HR-MAS MRS analysis.Results: Ex vivo HR-MAS MRS identified glycine,alanine, free choline, and triglycerides as possiblemolecular markers related to the human gastric mucosadifferentiation toward preneoplastic and neoplasticconditions. Ultrastructural studies of autoimmuneatrophic gastritis and gastric adenocarcinoma revealedlipid accumulations intracellularly and extracellularlyassociated witha severe prenecrotic hypoxia and mitochondriadegeneration.Conclusions: This is the first report of synergicapplications of ex vivo HR-MAS MRS and electronmicroscopy in studying the human gastric mucosadifferentiation. This research provides useful informationabout some molecular steps involved in gastriccarcinogenesis. The biochemical data obtained ongastric pathologic tissue could represent the basis forclinical applications of in vivo MRS

2008 - Discrimination of healthy and neoplastic human colon tissues by ex vivo HR-MAS NMR spectroscopy and chemometric analyses [Abstract in Atti di Convegno]
V., Righi; Durante, Caterina; Cocchi, Marina; C., Calabrese; V., Tugnoli; Mucci, Adele; Schenetti, Luisa
abstract

The metabolic profile of human healthy and neoplastic colorectal tissues was obtained using ex vivo High-Resolution Magic Angle Spinning (HR-MAS) NMR spectroscopy. Principal Components Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA) were applied to NMR data in order to highlight the biochemical differences between healthy and neoplastic colorectal tissues.

2008 - Effect of alkylsulphanyl substituent on the performance of polythiophene as donor material for bulk heterojunction solar cells [Abstract in Atti di Convegno]
P., Morvillo; E., Bobeico; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Polymer solar cells have evolved as a promising cost-effective alternative to siliconbasedsolar cells. However, low efficiency of these plastic solar cells limits their feasibility forcommercial use. The efficiencies of polymer photovoltaic cells got a major boost with theintroduction of the bulk heterojunction (BHJ) concept consisting of an interpenetrating network ofelectron donor and acceptor materials. In this work we describe the preparation of BHJ organic solarcells using blend films of poly[4,4’-bis(alkylsulfanyl)-2,2’-bithiophene] (PST) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM). Photovoltaic cells were prepared with a layersandwiched between electrodes with different work functions. We made a comparative study of theelectrical behaviour of different devices to investigate the influence of different fabricationconditions (donor/acceptor ratio, solvent, layer thickness, device annealing, etc.). The electricalperformance of the devices were compared with the corresponding one prepared using a blend ofcommercial poly(3-hexylthiophene) (P3HT) and PCBM. The quantum efficiency of the devicefabricated with PST/PCBM blend shows a better response in the visible region compared to the onewith P3HT/PCBM. Theoretical calculations on PST and P3HT were also carried out to explain theeffect of the alkylsulphanyl substituent (compared to hexyl one) on the geometry, band gap andHOMO/LUMO levels of polythiophene.

2008 - Electrodeposition of carbon nanotube semi-transparent thin films: A facile route for preparing photoactive polymeric hybrid materials [Articolo su rivista]
L., Valentini; D., Bagnis; Cagnoli, Rita; Mucci, Adele; Schenetti, Luisa; J., Kenny
abstract

In this work we report how the plasma treatment of electrophoretically deposited single-walled carbon nanotubes (e-SWCNTs) enabled us to obtain semi-transparent thin films used as anodes for the development of organic solar cells. Combining plasma treated e-SWCNT network with a conducting polymer (poly[7-(thien-3-ylsulfanyl)heptanoic acid]-co-thiophene), an increase of the open-circuit voltage and of the short-circuit current density was observed. We attribute this effect to an enhanced hole collection by the nanotube electrode due to their short aspect ratiopermitting a better interpenetration of the polymer.

2008 - Influence of substituents on the behaviour of polythiophene as donor in polymer-fullerene solar cells [Relazione in Atti di Convegno]
H. C., Neitzert; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; A., De Sio; A., Romano; E., Bobeico; P., Morvillo
abstract

Polymer solar cells have evolved as a promising cost-effective alternative to silicon-based solar cells.However, low efficiency of these plastic solar cells limits their feasibility for commercial use. The efficiencies ofpolymer photovoltaic cells got a major boost with the introduction of the bulk heterojunction (BHJ) conceptconsisting of an interpenetrating network of electron donor and acceptor materials.In this work we describe the preparation of BHJ organic solar cells using blend films of poly[4,4’-bis(alkylsulfanyl)-2,2’-bithiophene] (P3ST) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM). Photovoltaic cells wereprepared with a layer sandwiched between electrodes with different work functions. The electrical performance ofthe devices were compared with the corresponding one prepared using a blend of commercial poly(3-hexylthiophene)(P3HT) and PCBM. The quantum efficiency of the device fabricated with P3ST/PCBM blend shows a betterresponse in the visible region compared to the one with P3HT/PCBM.

2008 - Metabolic profiles of healthy and neoplastic human colorectal tissues studied by ex vivo HR-MAS MRS [Relazione in Atti di Convegno]
V., Righi; Mucci, Adele; Schenetti, Luisa; C., Calabrese; Cocchi, Marina; Durante, Caterina; V., Tugnoli
abstract

The metabolic profile of human healthy and neoplastic colorectal tissues was obtained through ex vivo HR-MAS MRS and studied through chemometric analyses.

2008 - Neoplasms of the gastro-intestinal tract characterized by HR-MAS NMR [Abstract in Atti di Convegno]
Mucci, Adele; V., Righi; C., Calabrese; Cocchi, Marina; Durante, Caterina; V., Tugnoli; Schenetti, Luisa
abstract

The results of our studies (HR-MAS NMR and statistical analysis) on healthy stomach and colon mucosa, and on gastric and colon adenocarcinomas are presented.

2008 - New Aminoalkylsulfanyl Polythiophenes: Organic and Water Soluble Polymers [Abstract in Atti di Convegno]
Preti, Lisa; Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

The synthesis and characterization of organic and water soluble aminoalkylsulfanyl polythiophenes are reported.

2008 - Organic- and Water-Soluble Aminoalkylsulfanyl Polythiophenes [Articolo su rivista]
Cagnoli, Rita; M., Lanzi; Libertini, Emanuela; Mucci, Adele; L., Paganin; Parenti, Francesca; Preti, Lisa; Schenetti, Luisa
abstract

Six new aminoalkylsulfanyl polythiophenes (PTs), namely PTNHBoc, PTNMeBoc, PTNH2,PTNHMe, PTNMe2, and PTN+Me3, were synthesized. Four of them were obtained through Stille coupling, whereasPTNH2 and PTNHMe were obtained through deprotection via N-Boc precursors. The solubility changes goingfrom the protected amines to the quaternary ammonium salt. All the polymers are soluble in DMSO and DMF.PTNHBoc and PTNMeBoc are also soluble in CHCl3, CH2Cl2, THF, and DMPU; PTNH2 and PTNHMe aresoluble in CH3OH, whereas PTNMe2 and PTN+Me3 are soluble both in CH3OH and in H2O. These PTs show atendency toward microaggregation in solution that does not represent an obstacle to their solubility. NMR, UV-vis,and XRD results prove that they are able to reach very high conjugation lengths and ordered conformations, notonly in the solid state but also in solutions of good solvents.

2008 - Preparation of the Maleic Anhydride Nucleus from Dichloro γ-Lactams: Focus on the Role of the N-Substituent in the Functional Rearrangement and in the Hydrolytic Steps [Articolo su rivista]
Ghelfi, Franco; M., Pattarozzi; Roncaglia, Fabrizio; A. F., Parsons; F., Felluga; Pagnoni, Ugo Maria; E., Valentin; Mucci, Adele; Bellesia, Franco
abstract

The preparation of the 3,4-dialkyl-substituted maleic anhydride nucleus, through the functional rearrangement of dichloro γ-lactams, allowed the comparison of various N-substituents in the functional rearrangement step. The 2-pyridyl group proved to be the most appropriate N-substituent for the hydrolysis of the 5-methoxy-1,5-dihydro-2H-pyrrol-2-one intermediate into the 5-hydroxy adduct, and for the hydrolysis of the maleimide nucleus into the maleic anhydride. The oxidation of the 5-hydroxy-1,5-dihydro-2H-pyrrol-2-one into the corresponding maleimide was achieved with manganese(IV) oxide.

2008 - Quantitative Magic Angle Spinning detection of deuteration in small biopsies of rat brain [Abstract in Atti di Convegno]
R., Fayos; V., Righi; Mucci, Adele; Schenetti, Luisa; S., Cerdán
abstract

A novel approach, involving 1D and 2D 2H and 1H-2H HR-MAS methodologies to investigate quantitatively 1H-2H turnover in small brain biopsies, is reported. The 1H-2H exchange of specific metabolite protons upon feeding rats with D2O is studied.

2008 - Sintesi e Caratterizzazione di Octatiofeni Funzionalizzati con Gruppi Ionici o Ionizzabili [Abstract in Atti di Convegno]
Preti, Lisa; Parenti, Francesca; Mucci, Adele; Schenetti, Luisa
abstract

Sono riportate la sintesi, tramite accoppiamento ossidativo, e la caratterizzazione di octatiofeni recanti in beta catene alchilsulfaniliche funzionalizzate con gruppi COOH e NH2.

2008 - Strategies to Reduce Inter-chain Aggregation and Fluorescence Quenching in Alternated Multilayers of a Polythiophene [Articolo su rivista]
Lodi, Andrea; Caselli, Monica; Zanfrognini, Barbara; Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Ponterini, Glauco
abstract

Electrostatically self-assembled multilayers of a fluorescent carboxyalkylsulfanyl polythiophene and poly(diallyldimethylammonium) were prepared using the layer-by-layer deposition approach and were structurally characterized by linear dichroism and atomic-force microscopy. Steady-state measurements revealed that fluorescence was quenched relative to the solution behaviour. The emission quantum yield was found to increase upon decreasing the polymer concentration in the dipping solution as well as by codepositing polythiophene with another polyanion, poly(sodium-4-styrenesulfonate). Fluorescence quenching was therefore attributed to the formation of non-emitting inter-chain aggregate exciton traps.Intercalation of polythiophene layers with non-emitting polymers having larger energy gaps did not result in enhanced fluorescence, thus suggesting negligible polythiophene aggregation and exciton migration across different layers. At best, we could obtain quantum yields around 0.1–0.15, about half the solution value but almost two orders of magnitude larger than found with cast or spin-cast films.

2008 - Synthesis and Characterization of ionic or ionisable octithiophenenes [Abstract in Atti di Convegno]
Preti, Lisa; Parenti, Francesca; Mucci, Adele; Schenetti, Luisa
abstract

Oligothiophenes (OTs) are materials with a precisely defined chain and conjugation length and they are usually more soluble than polymers and stable in various redox states. OTs are important molecules for applications in electronic devices, such as Field Effect Transistors (FETs), Organic Light-Emitting Diodes (OLEDs), photovoltaic cells, and sensors.2 Derivatisation of PTs with ionic or ionisable groups in the side chains provides internal charge compensation (or self-doping) generated during redox processes,3 as well as imparts water solubility. Thanks to these hydrophilic properties, ionic OTs could be able to interact with different ionic and biological molecules. This characteristic makes them interesting for applications as chemo- and bio-sensors. These applications require water-compatible materials, in the form of conjugated (and sometimes luminescent) polyelectrolytes, able to detect biomolecules through their impact on the conditions, for photoinduced charge or excitation transfer.4

2007 - Amminoalchilsulfanil politiofeni: come modulare la solubilità variando la sostituzione amminica [Abstract in Atti di Convegno]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Nuovi politiofeni ammino funzionalizzati sono stati sintetizzati tramite accoppiamento di Stille di opportuni monomeri.

2007 - Approccio biomometico alla sintesi di composti diterpenici a scheletro clerodanico [Abstract in Atti di Convegno]
Preti, Lisa; Mucci, Adele; Schenetti, Luisa; V., Lee; R. M., Adlington; J. E., Baldwinn
abstract

E' presentata la sintesi di un derivato diterpenico a scheletro clerodanico.

2007 - Bulk heteojunction solar cells using a novel polybithiophene polymer [Abstract in Atti di Convegno]
P., Morvillo; E., Bobeico; C., Privato; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

In this work we describe the preparation of BHJ organic solar cells using blend films of poly[4,4’-bis(alkylsulfanyl)-2,2’-bithiophene] (PST) and 1-(3- methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM). Photovoltaic cells were prepared with a layer sandwiched between electrodes with different work functions. We made a comparative study of the electrical behaviour of different devices to investigate the influence of different fabrication conditions (donor/acceptor ratio, solvent, layer thickness, device annealing, etc.).

2007 - Dotap/Udca vesicles: novel approach in oligonucleotide delivery [Articolo su rivista]
Ruozi, Barbara; Battini, Renata; Montanari, Monica; Mucci, Adele; Tosi, Giovanni; Forni, Flavio; Vandelli, Maria Angela
abstract

The relatively hydrophilic bile acid, ursodeoxycholic acid (UDCA), was used as additive to DOTAP cationic liposomes to evaluate the effect on the cellular uptake of an oligonucleotide. Nuclear magnetic resonance studies were applied to estimate the relative amount of incorporated UDCA into the lipidic bilayers. The interaction between the new formulations and 5’fluorescein conjugated 29-mer phosphorothioate oligonucleotide (PS-ODN) was studied using gel electrophoresis experiments. Besides, DOTAP or DOTAP/UDCA vesicles (MixVes; DOTAP/UDCA 1:0.25, 1:0.5, 1:1 and 1:2 molar ratio) were complexed with PS-ODN and tested after transfections the cellular uptake and the localization of the oligo in HaCaT cell line by the use of cytofluorimetric and confocal microscopic analysis. DOTAP lipid formulated in presence of defined amount of UDCA forms more stable, flexible and active MixVes. In particular, the MixVes at 1:0.25 and 1:0.5 molar ratio increase and modify the cellular uptake of PS-ODN if compared with DOTAP liposomes 3 h after the transfection studies. Besides, the in vitro data suggest that these new formulations are not toxic.

2007 - Ex vivo HR-MAS Magnetic Resonance Spectroscopy of Normal and Malignant Human Renal Tissues [Articolo su rivista]
V., Righi; Mucci, Adele; Schenetti, Luisa; M. R., Tosi; W. F., Grigioni; B., Corti; A., Bertaccini; A., Franceschelli; F., Sanguedolce; R., Schiavina; G., Martorana; V., Tugnoli
abstract

The aim of the present study was to examine themetabolic profile of normal and tumoral renal tissues by ex vivohigh resolution magic angle spinning magnetic resonancespectroscopy (HR-MAS MRS). Patients and Methods: Fivepatients, three affected by clear cell renal cell carcinoma (RCC)and two by papillary RCC, were examined. A radicalnephrectomy was performed in each. In all patients, fresh tissuesamples taken from normal cortex, normal medulla and tumorwere collected and analyzed by mono-dimensional HR-MASMRS. Results: The spectra of human normal cortex andmedulla showed the presence of differently distributed organicosmolytes as markers of a physiological renal condition. Themarked decrease or disappearance of these metabolites and thehigh lipid content (triglycerides and cholesteryl esters) is typicalof clear cell RCC, while papillary RCC are characterized by theabsence of lipids and very high amounts of taurine. Conclusion:This paper demonstrates that ex vivo HR-MAS MRS is a viableand powerful means of probing for molecular information inhuman normal and tumoral renal tissues. This research willconstitute the basis for a biochemical classification of renalneoplastic pathologies, especially for RCCs, which can be thusevaluated by in vivo MRS for clinical purposes. Moreover, thesedata may contribute to a better knowledge of the molecularprocesses for the basis of the onset of renal carcinogenesis.

2007 - HR-MAS NMR e analisi multivariata di neoplasie umane colo-rettali [Abstract in Atti di Convegno]
V., Righi; Durante, Caterina; Cocchi, Marina; V., Tugnoli; Mucci, Adele; Schenetti, Luisa
abstract

E' riportato uno studio basato sull'applicazione dell'HR-MAS NMR e dell'analisi multivariata a neoplasie umane colo-rettali.

2007 - Intermediates in the oxidative pathway from torulene to torularhodin in the red yeasts Cystofilobasidium infirmominiatum and C. capitatum (Heterobasidiomycetes, Fungi) [Articolo su rivista]
S., Herz; R. W. S., Weber; H., Anke; Mucci, Adele; Davoli, Paolo
abstract

Two red Cystofilobasidium spp. isolated from spring sap-flows of Betula pendula were analysed for their carotenoid content. In Cystofilobasidiuminfirmominiatum, three unusual pigments were detected and identified by structure elucidation as oxidised torulene derivatives.These included 16'-hydroxytorulene and torularhodinaldehyde, two carotenoids known so far only from chemical synthesis or aspostulated biosynthetic intermediates en route to torularhodin. Unprecedented formation of beta-apo-2'-carotenal was also observed. Theproduction of these pigments in pure culture was dependent on enhanced oxidative stress caused by cultivation in well-aerated (indented)flasks with or without 2% ethanol (16'-hydroxytorulene), or with 100 lM duroquinone (torularhodinaldehyde and beta-apo-2'-carotenal).Among these three pigments, only 16'-hydroxytorulene was detected in C. capitatum. Torularhodin, a common end product of carotenoidoxidation in red yeasts, was not produced by either species under any incubation conditions. Biosynthetic aspects of incompleteoxidation of torulene by these Cystofilobasidium spp. are discussed.

2007 - New Processable Aminoalkylsulfanyl Polythiophenes [Abstract in Atti di Convegno]
Cagnoli, Rita; Parenti, Francesca; Preti, Lisa; Mucci, Adele; Schenetti, Luisa
abstract

The synthesis and polymerization of novel alkylsulfanyl substituted thiophenes bearing amino end-groups is reported. The new materials were characterized by NMR, FT-IR, UV-Vis, XRPD and GPC.

2007 - Nuove formulazioni liposomiali per la veicolazione di materiale genico in cellule cheratinocito simili [Abstract in Atti di Convegno]
Ruozi, Barbara; Montanari, Monica; Tosi, Giovanni; Mucci, Adele; Vighi, Eleonora; Battini, Renata; Leo, Eliana Grazia; Forni, Flavio; Vandelli, Maria Angela
abstract

Nuove formulazioni liposomiali per la veicolazione di materiale genico in cellule cheratinocito simili

2006 - A new and effective route to (+/-)-botryodiplodin and (+/-)-epi-botryodiplodin acetates using a halogen atom transfer Ueno-Stork cyclization [Articolo su rivista]
L., DE BUYCK; C., Forzato; Ghelfi, Franco; Mucci, Adele; P., Nitti; Pagnoni, Ugo Maria; Af, Parsons; G., Pitacco; Roncaglia, Fabrizio
abstract

(+/-)-Botryodiplodin and (+/-)-epi-botryodiplodin acetates were prepared in good yields following a practical four step route. The method, for the construction of the strategic tetrahydrofuran ring, hinged on an unprecedented halogen atom transfer Ueno-Stork cyclization of an O-allyl alpha,alpha-dihalohemiacetal acetate, catalyzed by the redox complex CuCl/N,N,N ',N '',N ''-pentamethyldiethylenetriamine. (c) 2006 Elsevier Ltd. All rights reserved.

2006 - A poly(alkylsulfanyl)thiophene functionalized with carboxylic groups [Articolo su rivista]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Borsari, Marco; Lodi, Andrea; Ponterini, Glauco
abstract

Different routes, based on the Stille coupling, to the obtainment of a polythiophene bearing a carboxyhexylsulfanyl chain every two thiophene rings (PTCOOH) are here reported and discussed. Two PTCOOHs with different chain lengths were obtained: the shorter by hydrolysis of a polymeric ester precursor and the longer by direct Stille coupling from suitable monomers. They possess similar electrochemical properties but behave differently when aggregation and fluorescence are concerned. The PTCOOH obtained by hydrolysis is found to be fluorescent in a good solvent such as THF, and its fluorescence quantum yield decreases as the extent of aggregation increases. The polymer obtained by direct Stille coupling is less fluorescent, consistently with its proneness to aggregate. The PTCOOH obtained by hydrolysis is therefore more promising in view of the build-up of solid-state devices with exploitable fluorescence properties.

2006 - A short approach to chaetomellic anhydride A from2,2-dichloropalmitic acid: elucidation of the mechanism governingthe functional rearrangement of the chlorinatedpyrrolidin-2-one intermediate [Articolo su rivista]
Bellesia, Franco; Danieli, Chiara; L., De Buyck; R., Galeazzi; Ghelfi, Franco; Mucci, Adele; M., Orena; Pagnoni, Ugo Maria; A. F., Parsons; Roncaglia, Fabrizio
abstract

Chaetomellic anhydride A was efficiently attained in three steps, starting from 2,2-dichloropalmitic acid and 2-(3-chloro-2-propenylamino)pyridine. Atom transfer radical cyclisation selectively formed the cis-stereoisomer of the trichloropyrrolidin-2-one, which underwent a stereospecific functional rearrangement to form a substituted maleimide. The choice of 2-pyridyl, as ‘cyclisation auxiliary’ in the atom transfer radical cyclisation step, proved beneficial for hydrolysis of the maleimide to form the desired anhydride.

2006 - Caratterizzazione chimico-fisica e studi di stabilità di sistemi lipidici per il transfer genico [Abstract in Atti di Convegno]
Ruozi, Barbara; Tosi, Giovanni; Vighi, Eleonora; Leo, Eliana Grazia; Mucci, Adele; Schenetti, Luisa; Forni, Flavio; Vandelli, Maria Angela
abstract

Caratterizzazione chimico-fisica e studi di stabilità di sistemi lipidici per il transfer genico

2006 - Ex vivo HR-MAS MRS of human meningiomas: A comparison with in vivo H-1 MR spectra [Articolo su rivista]
V., Tugnoli; Schenetti, Luisa; Mucci, Adele; Parenti, Francesca; Cagnoli, Rita; V., Righi; A., Trinchero; L., Nocetti; C., Toraci; L., Mavilla; Trentini, Giampaolo; E., Zunarelli; M. R., Tosi
abstract

We report on the magnetic resonance spectroscopy (MRS) characterisation of different human meningiomas. Three histological subtypes of meningiomas (meningothelial, fibrous and oncocytic) were analysed both through in vivo and ex vivo MRS experiments. The ex vivo high-resolution magic angle spinning (HR-MAS) investigations, permitting an accurate description of the metabolic profile, are very helpful for the assignment of the resonances in vivo of human meningiomas and for the validation of the quantification procedure of in vivo MR spectra. By using one- and two-dimensional experiments, we were able to identify several metabolites in different histological subtypes of meningiomas. Our spectroscopic data confirmed the presence of the typical metabolites of these benign neoplasms and, at the same time, that meningomas with different morphological characteristics have different metabolic profiles, particularly regarding macromolecules and lipids. The ex vivo spectra allowed a better understanding and interpretation of the in vivo MR spectra, showing that the HR-MAS MRS technique could be a complementary method to strongly support the in vivo MR spectroscopy and increase its clinical potentiality.

2006 - Ex vivo HR-MAS Magnetic Resonance Spectroscopy of human gastric adenocarcinomas: A comparison with healthy gastric mucosa [Articolo su rivista]
Tugnoli, V; Mucci, Adele; Schenetti, Luisa; Righi, V; Calabrese, C; Fabbri, A; Di Febo, G; Tosi, Mr
abstract

The present study reports the characteristics of the biochemical profile of human gastric adenocarcinoma in comparison with that of healthy gastric mucosa, using ex vivo HR-MAS Magnetic Resonance Spectroscopy. Healthy human mucosa is mainly characterized by the presence of small metabolites (more than 50 identified) and macromolecules, whereas the adenocarcinoma spectra are dominated by the presence of signals due to triglycerides, whose content on the contrary is very low in healthy gastric mucosa. The use of spin-echo experiments enable us to detect some metabolites in the unhealthy tissues and to determine their variation with respect to the healthy ones. We have observed that the Cho:ChoCC ratio changes from 20:80 in the healthy tissues to 80:20 in the neoplastic gastric mucosa.

2006 - HR-MAS NMR spectroscopy in the characterization of human tissues: Application to healthy gastric mucosa [Articolo su rivista]
Schenetti, Luisa; Mucci, Adele; Parenti, Francesca; Cagnoli, Rita; Righi, V; Tosi, Mr; Tugnoli, V.
abstract

The HR-MAS is an ideal technique for the investigation of intact tissue specimens (10-50 mg) and permits the obtainment of spectra with a resolution comparable to that observed in solution in a time that does not exceed a half of an hour for a routine analysis. The potentialities of HR-MAS NMR spectroscopy in the identification of the metabolites characterizing the healthy gastric mucosa are here presented. The direct 1D H-1 NMR spectra enables only few metabolites to be confidently assigned, and the use of selected 2D experiments strongly amplify the analytical effectiveness of the technique.

2006 - Molecular Characterization of Human Neoplasms by Ex-Vivo HR-MAS Magnetic Resonance Spectroscopy [Abstract in Rivista]
V., Righi; Mucci, Adele; Schenetti, Luisa; M. R., Tosi; V., Tugnoli
abstract

The ex vivo HR-MAS NMR spectra of intact tissue specimens and correlate cellular metabolites with pathology.

2006 - Novel Thiophenic Copolymer as a Multi-Purpose Macromolecular Intermediate [Articolo su rivista]
L., Paganin; P., Costa Bizzarri; M., Lanzi; G., Cesari; F., Bertinelli; Cagnoli, Rita; Mucci, Adele
abstract

The preparation of a new thiophenic dimer partially derivatized with a bromohexylic chain is described. its polymerization under mild oxidative conditions leads to a polythiophene with a degree of functionalization Of 50% and highly soluble in organic solvents. The product has been fully characterized by FT-IR, H-1 and C-13 NMR using one and two-dimensional techniques as well as by SEC and thermal analysis. Solvatochromic effects of the new polymer have been investigated in different mixtures, underlining its self-assembling capability even in solvated states.

2006 - One-pot synthesis of symmetric octithiophenes from asymmetric beta-alkylsulfanyl bithiophenes [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Cagnoli, Rita; Benassi, Rois; Passalacqua, Alessio; Preti, Lisa; Schenetti, Luisa
abstract

Starting from 4-(octylsulfanyl)-2,2'-bithiophene, 4-bromo-4'-(octylsulfanyl)-2,2'-bithiophene, 4-iodo-4'-(octylsulfanyl)-2,2'-bithiophene, 4-bromo-4'-[(S)-2-methylbutylsulfanyl]-2,2'-bithiophene, and 4-iodo-4'-[(S)-2-methylbutylsulfanyl]-2,2'-bithiophene, a new series of symmetrically beta-substituted octithiophenes were synthesized by one-pot oxidative coupling with FeCl3. The octithiophenes obtained are soluble in common organic solvents and show different solvatochromic properties depending on the substitution type. In particular, the bromine atom exerts a positive influence on the supramolecular organization: the brominated octithiophenes display high filmability, solvatochromism, and CD induced by aggregation (when the chiral 2-methylbutylsulfanyl group is present), properties usually observed for polythiophenes. Density functional theory (DFT) calculations were carried out an a model bithiophene (4-substituted with a methylsulfanyl group) in order to understand the possible mechanism of the growth, the regiochemistry, and the reason for the polymerization leads to an octithiophene.

2006 - Sistemi lipidici per il transfer genico: sintesi di nuove molecole per la progettazione di vettori sintetici efficaci [Relazione in Atti di Convegno]
Ruozi, Barbara; Costantino, Luca; Gandolfi, Francesca; Vighi, Eleonora; Leo, Eliana Grazia; Mucci, Adele; Tosi, Giovanni; Vandelli, Maria Angela
abstract

Sistemi lipidici per il transfer genico: sintesi di nuove molecole per la progettazione di vettori sintetici efficaci

2006 - Studio comparativo del metabolismo di neoplasie cerebrali mediante spettroscopia RM in vivo ed ex vivo HR-MAS [Abstract in Rivista]
V., Tugnoli; A., Bacci; R., Ricci; Schenetti, Luisa; Mucci, Adele; V., Righi; N., Acciarri; R., Agati; S., Battaglia; M., Leopardi
abstract

Abbiamo esaminato 10 pazienti portatori di tumori cerebrali (glioblastomi, meningiomi, metastasi, emangioblastoma, astrocitoma pilocitico, cisti colloide) mediante spettroscopia RM in vivo ed ex vivo HR-MAS.

2006 - Symmetric Octithiophenes: One-Pot Synthesis and ElectrochemicalProperties [Abstract in Atti di Convegno]
Preti, Lisa; Mucci, Adele; Schenetti, Luisa; Parenti, Francesca; Cagnoli, Rita; Passalacqua, Alessio; Benassi, Rois; Fontanesi, Claudio; Ferrarini, Paolo; F., Paolucci; M., Marcaccio; C., Bruno
abstract

sono stati riportati le sintesi di octatiofeni simmentrici ottenuti per accoppiamento ossidativo con FeCl3 e la loro caratterizzazione spettroscopica ed elettrochimica

2006 - Synthesis of asymmetric beta-alkylsulfanyl bithiophenes as precursors for symmetric octithiophenes [Abstract in Atti di Convegno]
Schenetti, Luisa; Mucci, Adele; Parenti, Francesca; Cagnoli, Rita; Preti, Lisa
abstract

The synthesis of 4-alkylsulfanyl bithiophenes, based on Stille coupling reaction, is reported.

2006 - The Coline Metabolite Pattern Detected by 1H HR MAS Accurately Discriminates between High and Low Human Glioma Grade [Abstract in Atti di Convegno]
V., Righi; P., Lopez Larrubia; P., Sanchez Garcia; V., Tugnoli; Schenetti, Luisa; Mucci, Adele; J., Paz; J. M., Roda; S., Cerdan; M. L., Garcia Martin
abstract

The Coline Metabolite Pattern was studied through 1H HR MAS NMR with the aim of discriminating between High and Low Human Glioma Grade

2005 - 2-Hydroxytorularhodin, a New Xanthophyll from the Red Yeast Sporobolomyces coprosmae [Articolo su rivista]
Weber, Rws; Madhour, A; Anke, H; Mucci, Adele; Davoli, Paolo
abstract

A new hydroxylated carotenoic acid was isolated from the red yeast Sporobolomlyces coprosinae and unambiguously identified as 2-hydroxytorularhodin (1), i.e., (all-E)-3',4'-didehydro-2-hydroxy-beta-psi-carotcn-16'-oic acid, by application of extensive 1D and 2D NMR techniques (gCOSY, gHSOC gHMBC DQS, gTOSY, and ROESY). Hydroxylation of carotenoids at C(2) is uncommon in nature, very rare in fungi, and unprecedented for torularhodin.

2005 - A Theoretical Investigation on the Oligomerization of 4-Alkylsulfanyl bithiophene [Abstract in Atti di Convegno]
Passalacqua, Alessio; Parenti, Francesca; Cagnoli, Rita; Mucci, Adele; Schenetti, Luisa; Benassi, Rois
abstract

Desnity functional B3PW91 with Midix basis set was performed in order to investigate various mechanisms of growth of a symmetric octithiophene.

2005 - A comparison between in vivo and ex vivo HR-MAS H-1 MR spectra of a pediatric posterior fossa lesion [Articolo su rivista]
Tugnoli, V; Schenetti, Luisa; Mucci, Adele; Nocetti, L; Toraci, C; Mavilla, L; Basso, G; Rovati, R; Tavani, F; Zunarelli, E; Righi, V; Tosi, Mr
abstract

The present case report was aimed at identifying the molecular profile characteristic of a primitive neuroectodermal tumor (PNET) in a 3-year-old child affected by a lesion localized in the cerebellar region. The histological diagnosis was medulloblastoma. In vivo single voxel H-1 magnetic resonance spectroscopy (MRS) shows high specificity in detecting the main metabolic alterations in the primitive cerebellar lesion; a very high amount of the choline-containing compounds and very low level of creatine derivatives and N-acetylaspartate. Ex vivo high resolution magic angle spinning (HR-MAS) H-1 magnetic resonance spectroscopy, performed at 9.4 Tesla on the neoplastic specimen collected during surgery, allows for the unambiguous identification of several metabolites giving a more in-depth evaluation of the metabolic pattern of the lesion. The ex vivo HR-MAS MR spectra show that the spectral detail is much higher than that obtained in vivo and that, for example, myo-inositol, taurine and phosphorylethanolamine contribute to the in vivo signal at 3.2 ppm, usually attributed to choline-containing compounds. In addition, the spectroscopic data appear to correlate with some morphological features of the medulloblastoma. Consequently, the present study shows that ex vivo HR-MAS H-1 MRS is able to strongly improve the clinical possibility of in vivo MRS and can be used in conjunction with in vivo spectroscopy for clinical purposes.

2005 - Acidi colici nella preparazione di liposomi cationici per la transfezione in cellule HaCaT [Abstract in Atti di Convegno]
Ruozi, Barbara; Battini, Renata; Mucci, Adele; Tosi, Giovanni; Forni, Flavio
abstract

Acidi colici nella preparazione di liposomi cationici per la transfezione in cellule HaCaT

2005 - Biosynthesis of the xanthophyll plectaniaxanthin as a stress response in the red yeast Dioszegia (Tremellales, Heterobasidiomycetes, Fungi) [Articolo su rivista]
Madhour, A; Anke, H; Mucci, Adele; Davoli, Paolo; Weber, Rws
abstract

Carotenoid biosynthesis was examined in a phylloplane yeast identified by ITS, 18S and 28S rDNA analysis as a Dioszegia sp. close to D. takashimae. In well-aerated flask or fermentor cultures, this strain produced essentially a single pigment confirmed as the xanthophyll plectaniaxanthin by NMR analysis, at concentrations of 103-175 mu g g(-1) biomass dry weight. Detailed studies showed increases in plectaniaxanthin concentrations in the presence of 5 mM hydrogen peroxide (1.8-fold), 50 and 100 mu M duroquinone (3.1- and 3.7-fold, respectively), and 2% ethanol (4.9-fold). Whereas oxidative stress is known to enhance the biosynthesis of torularhodin or astaxanthin in other red yeasts where they are associated with an antioxidant function, this is the first report implicating plectaniaxanthin in a similar role. At reduced aeration, biosynthesis of plectaniaxanthin was suppressed and its putative precursor gamma-carotene accumulated. The carotenoid cyclase inhibitor nicotine (5-20 mM) inhibited plectaniaxanthin formation, with lycopene accumulating stoichiometrically. Hydroxy groups at C-1´ and C-2´ therefore seem to be introduced late in plectaniaxanthin biosynthesis, following cyclization of the P-ionone ring.

2005 - Combining single wall carbon nanotubes and photoactive polymers for photoconversion [Articolo su rivista]
G. M. A., Rahman; D. M., Guldi; Cagnoli, Rita; Mucci, Adele; Schenetti, Luisa; L., Vaccari; M., Prato
abstract

A combination of van der Waals and electrostatic interactions was used to integrate SWNT and a suitably functionalized polythiophene into nanostructured ITO electrodes. In the resulting electron donor/ acceptor nanocomposites, polythiophene represents the light-harvesting chromophore that readily donates an excited-state electron to the ground-state electron-accepting SWNT. Upon illumination, monochromatic incident photoconversion efficiencies between 1.2 and 9.3% were determined for single and eight-sandwiched layers, respectively.

2005 - High-Resolution Magic Angle Spinning 1H-NMR Spectroscopy Studies of Human Extra-cerebral Neoplasms [Abstract in Atti di Convegno]
V., Righi; V., Tugnoli; Schenetti, Luisa; Mucci, Adele; L., Nocetti; C., Toraci; L., Mavilla; Basso, Gianpaolo; R., Rovati; F., Tavani; E., Zunarelli; R., Tosi
abstract

We present the first results of a study on neoplastic extra-cerebral surgical specimen. 1H presaturated, CPMG, diffusion, COSY, TOSCY spectra were discussed.

2005 - Laetiporic acids, a family of non-carotenoid polyene pigments from fruit-bodies and liquid cultures of Laetiporus sulphureus (Polyporales, Fungi) [Articolo su rivista]
Davoli, Paolo; Mucci, Adele; Schenetti, Luisa; R. W. S., Weber
abstract

The non-isoprenoid polyene laetiporic acid A, recently described from fruit-bodies of the wood-rotting fungus Laetiporus sulphureus, was found to be the major orange pigment also in mycelium grown in liquid culture. Its formation was variable, ranging from 0.1 to 6.7 mg/g dry weight in three strains, all of which were identified as L. sulphureus by ITS rDNA sequence analysis. A second pigment, 2-dehydro-3-deoxylaetiporic acid A, is also described and fully characterized by NMR spectroscopy. Two further minor pigments, laetiporic acids B and C, were produced in liquid culture. These resemble laetiporic acid A but are enlarged by two and four carbon atoms, respectively, resulting in chromophores with I I or 12 instead of 10 conjugated double bonds as described for laetiporic acid A. Since fruit-bodies of L. sulphureus are edible, laetiporic acids might hold potential as food colourants.

2005 - Liposome evolution: novel approach in gene transfer [Abstract in Atti di Convegno]
Ruozi, Barbara; Battini, Renata; Mucci, Adele; Schenetti, Luisa; Tosi, Giovanni; Forni, Flavio; Vandelli, Maria Angela
abstract

Liposome evolution: novel approach in gene transfer

2005 - Metabolic evaluation of human meningiomas by magic angle spinning ex vivo proton magnetic resonance spectroscopy [Abstract in Rivista]
V., Tugnoli; Mucci, Adele; V., Righi; Schenetti, Luisa; M. R., Tosi
abstract

HR-MAS NMR spectroscopy was applied on meningioma samples. 1H presaturated, COSY and TOCSY spectra were acquired. Several low weight metabolites were detected: glutathione, glutammine, isoleucine, valine, leucine, lysine, arginine, threonine, aspartate, glycine, beta-alanine, creatine, taurine, hipo-taurine, glucose, myoinositol, scylloinositol, mannitol and choline containing compounds.

2005 - Nuova sintesi della (+/-)-Botriodiplodina attraverso ciclizzazione di Ueno-Stork a trasferimento di atomo [Abstract in Atti di Convegno]
Roncaglia, Fabrizio; L., De Buyck; Bellesia, Franco; C., Forzato; Ghelfi, Franco; L., Goldoni; Mucci, Adele; Pagnoni, Ugo Maria; A. F., Parsons; E., Valentin
abstract

E' presentata una nuova sintesi della (+/-)-Botriodiplodina attraverso ciclizzazione di Ueno-Stork a trasferimento di atomo

2005 - Palladium(II) derivatives of alkylsulfanyl substituted thiophenes as precursors of inorganic polymers: Spectroscopic, electrochemical investigations and X-ray crystal structure of trans-PdCl2[3-(butylsulfanyl)thiophene](2) [Articolo su rivista]
Antolini, Luciano; G., Minghetti; Mucci, Adele; Parenti, Francesca; Pigani, Laura; G., Sanna; Seeber, Renato; Zanardi, Chiara
abstract

Palladium(II) complexes with two thiophene derivatives bearing alkylsulfanyl chains, i.e., 3-(n-butylsulfanyl)thiophene and 4,4´-bis(n-butylsulfanyl)-2,2´-bithiophene, are synthesised and spectroscopically and electrochemically characterised. The molecular structure of PdCl2[3-(n-butylsulfanyl)thiophene]2 was determined by X-ray analysis. The properties of the complexes have been compared with those of PdCl2[3,3´-bis(n-butylsulfanyl)-2,2´-bithiophene] and of a conductive polymer partially coordinated with Pd(II), previously synthesised by us. We found that Pd(11) ions can coordinate sulfanyl sulfur atoms both in cis and trans configuration, leading to a reticulate material, where some kind of interchain bridging may be reasonably supposed to enhance the bulk conductivity.

2005 - Polymerization of Cysteine Functionalized Thiophenes [Articolo su rivista]
Cagnoli, Rita; M., Lanzi; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Different synthetic pathways leading to polythiophenes (PTs) containing units derived from methyl N-(tert-butoxycarbonyl)-S-3-thienyl-L-cysteinate (1) and methyl N-(tert-butoxycarbonyl)-S-(2-thien-3-ylethyl)-L-cysteinate (2) were investigated. The oxidative coupling with FeCl3 applied to N-deprotected monomer 1 generates a chemically fleeting PT, whereas when applied to N-deprotected monomer 2 generates a mixture of oligomers. Two co-polymers bearing cysteine moieties, poly{[methyl N-(tert-butoxycarbonyl)-S-3-thienyl-L-cysteinate]-cothiophene}(co-PT1) and poly{[methyl N-(tert-butoxycarbonyl)-S-(2-thien-3-ylethyl)-L-cysteinate]-co-thiophene} (co-PT2), were eventuallysynthesized through Stille coupling of 2,5-bis(trimethylstannyl)thiophene and 2,5-dibromo derivative of compound 1 and through the post-functionalization with protected cysteine of a tosylate co-polymer, poly{[2-(3-thienyl)ethyl 4-methylbenzenesulfonate]-co-thiophene}(co-PTTs). UV–vis, CD, NMR and GPC analyses evidenced that these polymers are able to form chiral self-assembling structures, due to the formation of a hydrogen bond network and to p-stacks, not only in the solid state but also in solution.

2005 - Preparation and characterization of thiophene copolymers with second order non-linear optical properties [Articolo su rivista]
C., Della Casa; A., Fraleoni Morgera; M., Lanzi; P., Costa Bizzarri; L., Paganin; F., Bertinelli; Schenetti, Luisa; Mucci, Adele; M., Casalboni; F., Sarcinelli; A., Quatela
abstract

Azobenzene-substituted polythiophenes were prepared by copolymerization of 3-alkylthiophenes functionalized with an azo-chromophore and 3-alkylthiophenes as plastifying comonomers to improve solubility. Monomers with different oligomethylenic spacer and alkylic chain lengths were synthesized and copolymerized via FeCl3 oxidative polymerization. Polymer soluble fractions were characterized by H-1 and C-13 NMR, FTIR, UV-Vis spectroscopy, and GPC, DSC and TGA. Second-order non-linear optical properties were measured by the second harmonic generation technique.

2005 - Sintesi della (+/-)-Botriodiplodina e della sua forma Epi attraverso una ciclizzazione di Ueno-Stork a trasferimento di atomo [Abstract in Atti di Convegno]
Roncaglia, Fabrizio; L., De Buyck; Bellesia, Franco; C., Forzato; Ghelfi, Franco; L., Goldoni; Mucci, Adele; Pagnoni, Ugo Maria; A. F., Parsons; E., Valentin
abstract

E' riportata la sintesi della (+/-)-botriodiplodina e della sua forma Epi attraverso una ciclizzazione di Ueno-Stork a trasferimento di atomo

2005 - Sintesi di derivati politiofenici ad alta versatilità strutturale [Abstract in Atti di Convegno]
L., Paganin; P., Costa Bizzarri; M., Lanzi; G., Cesari; F., Bertinelli; Cagnoli, Rita; Mucci, Adele
abstract

Sono riportate la sintesi e la caratterizzazione di derivati politiofenici ad alta versatilità strutturale.

2005 - Studio di una via più versatile per la preparazione di nuclei 2,5-furandionici disostituiti [Abstract in Atti di Convegno]
L., De Buyck; Ghelfi, Franco; Mucci, Adele; Pagnoni, Ugo Maria; A. F., Parsons; Pinetti, Adriano; Roncaglia, Fabrizio
abstract

Si riporta lo studio di una via più versatile per la preparazione di nuclei 2,5-furandionici disostituiti

2005 - Synthesis of two novel cysteine-functionalized thiophenes [Articolo su rivista]
Cagnoli, Rita; M., Lanzi; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

The synthetic approach to methyl N-(tert-butoxycarbonyl) -S- (3-thienyl)-L-cysteinate (1) and methyl N-(tert-butoxycarbonyl)-S-[2-(3-thienyl)ethyl]-L-eysteinate (2) through tosylate intermediates is reported and discussed. These compounds, which combine the properties of the cysteine side-chain with those of the thiophene ring represent both potential bioactive molecules and interesting synthons for the development of new materials.

2005 - What is NMR Spectroscopy? A Preliminary Insight into NMR Spectroscopy [Capitolo/Saggio]
Schenetti, Luisa; Mucci, Adele
abstract

Nuclear Magnetic Resonance (NMR) is a very powerful tool for the structure determination of biomolecules and natural compounds, for the study of tissue extracts or intact tissues, and for the obtainment of detailed three-dimensional maps of the human body and organs. In the field of biomedicine, the two areas of NMR are represented by Magnetic Resonance Imaging (MRI) and by the multi-branched Magnetic Resonance Spectroscopy (MRS), where MRS is the acronym utilised in place of NMR. MRI uses the strong signal from water protons (1H) to provide detailed anatomical maps and has proven to be an indispensable tool for both researchers and clinicians, but its specificity in defining the pathology is limited to only some diseases. NMR spectroscopy in its one- and two-dimensional version can be utilised to detect and assign the resonances observed in in-vitro extracts and ex-vivo biopsy samples, helping in disentangling the complex spectral pattern due to signal overlapping. This represent the first step in the individuation of the NMR biochemical markers representative of the healthy or pathological state of the tissue or organ. The results can then utilised at diagnostic and prognostic level in in-vitro and rx-vivo analyses. They also provide the rationale basis for the interpretation of in-vivo MRS studies.

2004 - A simple and efficient route to chaetomellic anhydride A: A potent natural Ras farnesyl-protein transferase inhibitor [Articolo su rivista]
L., De Buyck; Cagnoli, Rita; Ghelfi, Franco; G., Merighi; Mucci, Adele; Pagnoni, Ugo Maria; A. F., Parsons
abstract

A new and efficient approach to chaetomellic anhydride A has been devised starting from 2,2-dichloropalmitic acid. This involves the atom transfer radical cyclization of an N-alkyl-N-(3-chloro-2-propenyl)amide followed by rearrangement of the resulting trichloro-pyrrolidin-2-one.

2004 - Beta-alkylsulfanyl polythiophenes functionalized with carboxylic group [Abstract in Atti di Convegno]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

v. allegato

2004 - Biotransformation of resveratrol: synthesis of trans-dehydrodimers catalyzed by laccases from Myceliophtora thermophyla and from Trametes pubescens [Articolo su rivista]
S., Nicotra; Cramarossa, Maria Rita; Mucci, Adele; Pagnoni, Ugo Maria; S., Riva; Forti, Luca
abstract

Laccases from different sources have been used, for the first time, for the selective oxidation of the stilbenic phytoalexin transresveratrol (3,5,4´-trihydroxystilbene, 1a) on a preparative scale. Specifically, the enzymes from Myceliophtora thermophyla and from Trametes pubescens gave the dehydrodimer 2a in 31 and 18% isolated yields, respectively. These results compare favorably with the reported data for the chemically catalyzed dimerization of la (18% yields). The antioxidant properties of 2a have also been investigated.

2004 - Functional rearrangement of polychlorinated pyrrolidin-2-onesto 5-imino-lactams promoted by n-propylamine [Articolo su rivista]
Danieli, Chiara; Ghelfi, Franco; Mucci, Adele; Pagnoni, Ugo Maria; A. F., Parsons; M., Pattarozzi; Schenetti, Luisa
abstract

Abstract—The reaction of 4-methyl-pyrrolidin-2-ones, chlorinated at the C(3) and C(6) positions, with n-propylamine constitutes a new method for the preparation of 5-propylimino-pyrrolidin-2-ones or 3-pyrrolin-2-ones in generally good yields. The transformation involves a series of eliminations, substitutions and double bond shifts. This constitutes a remarkable example of a functional rearrangement.

2004 - La Risonanza Magnetica Nucleare all'Angolo Magico (HR-MAS) applicata su campioni di origine animale e vegetale [Articolo su rivista]
V., Righi; Parenti, Francesca; V., Tugnoli; Schenetti, Luisa; Mucci, Adele; Cagnoli, Rita; Mr, Tosi
abstract

Nuclear Magnetic Resonance (NMR) spectroscopy, widely employed for the identification and structural characterization of organic compounds, nowdays allows intact semisolid and solid samples, like animal and vegetable tissues, to be anlyzed thanks to the introduction of High Resolution Magic Angle Spinning (HR-MAS) probes. The results of a 1-H NMR HR-MAS study on cauliflower (Brassica oleracea) stem and on a chicker liver are reported.

2004 - Laetiporic acid, a new polyene pigment from the wood-rotting basidiomycete Laetiporus sulphureus (Polyporales, Fungi) [Articolo su rivista]
Rws, Weber; Mucci, Adele; Davoli, Paolo
abstract

A new pigment, laetiporic acid, has been isolated from fruit-bodies of the wood-rotting fungus Laetiporus sulphureus (sulfur shelf). Structure elucidation by application of extensive 2D NMR techniques permitted its identification as a polyene of non-isoprenoid origin. Laetiporic acid, which represents the main pigment in L. sulphureus basidiocarps, bears an unprecedented decaene skeleton as part of its chromophore and, interestingly, contains double bonds with a stable cis configuration.

2004 - Molecular characterization of human gastric mucosa by HR-MAS Magnetic Resonance Spectroscopy [Articolo su rivista]
V., Tugnoli; Mucci, Adele; Schenetti, Luisa; C., Calabrese; G., Di Febo; Rossi, Maria Cecilia; R., Tosi
abstract

The present study was aimed at identifying themolecular profile characteristic of the healthy humangastric mucosa.Ex vivo HR-MAS magnetic resonance spectroscopy performed at 9.4 Tesla (400.13 MHz for 1H) on gastric specimens collected during endoscopy, permits the identification of more than forty species giving a detailed picture of the biochemical pattern of the gastric tissues. These preliminary data will be used for a comparison with gastric preneoplastic and neoplastic situations. Moreover, the full knowledge of the biochemical pattern of the healthy gastrictissues is the necessary presupposition for the application of magnetic resonance spectroscopy directly in vivo.

2004 - Sintesi dell’acido chetomellico A, un antitumorale naturale inibitore della RAS farnesil-protein transferasi (FPTasi) [Abstract in Atti di Convegno]
L., De Buyck; Danieli, Chiara; Ghelfi, Franco; Mucci, Adele; Pagnoni, Ugo Maria; Pinetti, Adriano; A. F., Parsons
abstract

Si propone una nuova via sintetica per l'ottenimento dell’acido chetomellico A.

2004 - Sviluppo di nuovi sistemi liposomiali per la veicolazione di oligonucleotidi in cellule cheratinocito simili [Abstract in Atti di Convegno]
Ruozi, Barbara; Battini, Renata; Forni, Flavio; Mucci, Adele; Vandelli, Maria Angela
abstract

Sviluppo di nuovi sistemi liposomiali per la veicolazione di oligonucleotidi in cellule cheratinocito simili

2004 - Synthesis and Characterisation of New Polythiophenes Functionalised with Ionic Groups [Abstract in Atti di Convegno]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

The synthesis and characterisation of new polythiophenes functionalised with ionic or ionisable groups is reported

2004 - Synthetic utility of 2,2-dichlorocarboxylic acids [Abstract in Atti di Convegno]
L., De Buyck; Ghelfi, Franco; Mucci, Adele; Pagnoni, Ugo Maria; N., Dieltiens; A. F., Parsons
abstract

The synthetic utility of derivatives of 2,2-dichlorocarboxylic acids in radical cyclization reactions is shown.

2003 - A self-assembling polythiophene functionalised with a cysteine moiety [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

A new copolymer bearing a cysteine moiety, designed for molecular interaction, metal-ion-detection, and chiral recognition, was synthesized starting from the diborom derivative of methyl N-(tert-butoxycarbonyl)-S-thien-3-ylcysteinate and distannylthiophene through a Stille coupling reaction. UV-vis spectroscopy, circular dichroism, NMR spectroscopy, and gel permeation chromatography analyses evidenced that this polymer is able to form self-assembling structures, through the formation of a hydrogen-bond network, not only in the solid state but also in solution.

2003 - Complexes of Platinum(II) Containing Neutral and Deprotonated 9-Methyladenine. Synthesis, X-ray Structures, and NMR Studies on the Cyclic Trimer cis-[L2Pt{9-MeAd(−H)}]3(NO3)3 and the Dinuclear cis-[L2Pt(ONO2){9-MeAd(−H)}PtL2](NO3)2 (L = PMePh2) [Articolo su rivista]
B., Longato; L., Pasquato; Mucci, Adele; Schenetti, Luisa; E., Zangrando
abstract

The dinuclear hydroxo complex cis-[L2Pt(í-OH)]2(NO3)2 (L ) PMePh2, 1), in CH2Cl2, CH3CN, or DMF solution,deprotonates the NH2 group of 9-methyladenine (9-MeAd) to give the complex cis-[L2Pt{9-MeAd(-H)}]3(NO3)3, 2, which was isolated in good yield. The X-ray structure shows that the nucleobase binds symmetrically the metal centers through the N(1),N(6) atoms forming a cyclic trimer with Pt---Pt distances in the range 5.202(1)-5.382(1) Å. Dissolution of 2 in DMSO or DMF determines the partial (or total) dissociation of the cyclic structure to form several fragments. A multinuclear NMR analysis of the resulting mixture supports the presence of the mononuclear species cis-[L2Pt{9-MeAd(-H)}]+, 3, in which the deprotonated nucleobase chelates the metal center with the N(6),N(7) atoms. Addition of a stoichiometric amount of the nitrato complex cis-[L2Pt(ONO2)2] (L ) PMePh2, 4) to a DMSO or DMF solution of 2 affords quantitatively the diplatinated compound cis-[L2Pt(ONO2){9-MeAd(-H)}-PtL2](NO3)2, 5. The single-crystal X-ray analysis shows that the adenine behaves as a tridentate ligand bridgingtwo cis-L2Pt units at the N(1) and N(6),N(7) sites, respectively [Pt(1)-N(1) ) 2.109(5) Å, Pt(2)-N(6) ) 2.095(7) Å, Pt(2)-N(7) ) 2.126(7) Å]. The N(1)-bonded metal center completes the coordination sphere through an oxygen atom of a nitrate group, and its coordination plane is arranged orthogonally with respect the second one. The Pt-O distance [2.109(5) Å] is similar to those found in the nitrato complex 4 [2.110 Å, average]. The related complex cis-[{L2Pt(ONO2)}2(9-MeAd)](NO3)2, 6, containing the neutral adenine platinated at the N(1),N(7) atoms, was isolated and its stability in solution investigated by NMR spectroscopy. In DMSO, 6 undergoes decomposition forming a mixture of the species 4, 5, and the adenine mono- and bis-adducts cis-[L2Pt(9-MeAd)(DMSO)]2+, 7, and cis-[L2-Pt(9-MeAd)2]2+, 8, respectively. This last complex, quantitatively formed upon addition of 9-MeAd (Pt/adenine (1:2) to the mixture, was also isolated and characterized.

2003 - Coordination modes of 9-methyladenine in cis-platinum(II) complexes with dimethyl(phenyl)phosphanes as ancillary ligands - Synthesis and characterization of cis-[PtL2(9-MeAd)(2)](NO3)(2),cis-[PtL2{9-MeAd(-H)}](3)(NO3)(3), and cis-[L2Pt{9-MeAd(-H)}PtL2](NO3)(3) [Articolo su rivista]
B., Longato; L., Pasquato; Mucci, Adele; Schenetti, Luisa
abstract

Treatment of 9-methyladenine (9-MeAd) with cis[PtL2(NO3)(2)] (1) (L = PMe2Ph) in a 2:1 molar ratio generated the bis(adduct) cis-[PtL2(9-MeAd)(2)](NO3)(2) (2), which was isolated and fully characterized by multinuclear (H-1, P-31, C-13, Pt-195 and N-15) NMR analysis, which showed that the two nucleobases are selectively coordinated through the N1 atom. Small amounts of a mono(adduct) cis-[PtL2(S)(9-MeAd)](2+) (3) (S = solvent) and of a diplatinated species cis-[L2Pt(S){9MeAd(-H)]PtL2](3+) (4) are formed in DMSO solution when 9MeAd is present in smaller quantities than 1. Complex 3 is platinated at N1, with a solvent molecule representing the fourth ligand around the metal center. Complex 4 contains an adenine molecule deprotonated and platinated at N1,N6,N7, with two cis-L2Pt units bonded to nitrogen atom N1 and to nitrogen atoms N6 and N7, respectively. With increasing relative concentration of the nucleobase, both complexes 3 and 4 progressively convert into the bis(adduct) 2, the only species detectable in solution when the Ad/Pt molar ratio is 2:1. The trinuclear compound cis-[L2Pt{9-MeAd(-H)}](3)(NO3)(3) (5).

2003 - Copolimeri a base tiofenica: Sintesi e copolimerizzazione del 7-(3-tienilsulfanil)eptanonitrile [Abstract in Atti di Convegno]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Sono riportate la sintesi e copolimerizzazione del 7-(3-tienilsulfanil)eptanonitrile per l'ottenimento di copolimeri a base tiofenica

2003 - Radical ions from 3,3 ''',3 ''''-tris(butylsulfanyl)-2,2 ': 5 ',2 '': 5 '',2 ''',5 ''',2 '''': 5 '''',2 '''''-sexithiophene: An experimental and theoretical study of the p- and n-doped oligomer [Articolo su rivista]
A., Alberti; B., Ballarin; M., Guerra; D., Macciantelli; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Seeber, Renato; Zanardi, Chiara
abstract

The 3,3',3' tris(butylsulfanyl)-2,2':5,2:5,2',5',2:5, 2'- sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1(+circle) was evidenced by the H-1 NMR study in the presence of small quantities of trifluoroacetic acid (TFA). This approach allowed a comparison of the relative broadening of proton signals of 1, induced by the electron exchange process with traces of radical cation 1(+circle), and the hfc (hyperfine coupling) constants obtained from the EPR study and DFT calculations. In the radical cation, all of the heterocyclic sulphur atoms are not significantly involved in the delocalisation of the unpaired electron, whereas the opposite holds for the radical anion. Time-dependent DFT calculations reproduced well the wavelengths of the optical transitions observed in the spectroelectrochemical experiments for all the five oxidation states and support the formation of the dianion 1(2-).

2003 - Sintesi di Polimeri beta-sostituiti con catene alchil sulfaniliche funzionalizzate [Abstract in Atti di Convegno]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Sono riportate alcune sintesi di Polimeri beta-sostituiti con catene alchil sulfaniliche funzionalizzate e la caratterizzazione dei materiali ottenuti

2003 - Sintesi di Polimeri beta-sostituiti con catene alchil sulfaniliche funzionalizzate [Abstract in Atti di Convegno]
Cagnoli, Rita; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Sono riportate alcune sintesi di politiofeni beta-sostituiti con catene alchil sulfaniliche funzionalizzate

2003 - Sintesi semplificata dell’acido chetomellico A, antitumorale naturale inibitore della Ras farnesil-protein transferasi [Abstract in Atti di Convegno]
L., De Buyck; Bellesia, Franco; Ghelfi, Franco; G., Merighi; Mucci, Adele; Pagnoni, Ugo Maria; Pinetti, Adriano; A. F., Parsons
abstract

E' riportata una sintesi semplificata dell’acido chetomellico A, antitumorale naturale inibitore della Ras farnesil-protein transferasi.

2003 - The effect of Pd(II) coordination on the properties of an alkylsulfanyl substituted polythiophene. Comparison with the corresponding monomer [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Pigani, Laura; Seeber, Renato; Zanardi, Chiara; M. I., Pilo; N., Spano; M., Manassero
abstract

The synthesis of a conducting polymer partially coordinated with Pd(II) ions is reported. The aim is to study the influence of the metal on the properties of the material as a whole, which is very appealing for possible applications in the field of amperometric sensors. An alkylsulfanyl substituted polythiophene is used in this first approach, due to the well known affinity of the sulfur atom for soft metals. The interaction between the organic and inorganic moieties results in the easy formation of partially coordinated polymer. The presence of the metal ions is found to affect the chemical, physical, and electrochemical properties of the organicmacromolecules, owing to interactions between the polymer p-conjugation system and the metal d orbitals.Synthesis and characterisation of the relevant monomer complex helps to better understand the behaviour of the complex polymer-metal system.

2002 - A new polymer-like octathiophene. Synthesis and properties of 4,3'',4''''',4'''''''-tetrabromo-4',4''',3'''',3''''''-tetra(octylsulfanyl)-2,2':5',2'':5'',2''':5''', 2'''':5'''',2''''':5''''', 2'''''':5'''''',2''''''' -octathiophene [Abstract in Atti di Convegno]
Parenti, Francesca; A., Bellei; Mucci, Adele; Schenetti, Luisa
abstract

The oxidative polymerization of 4-bromo-4'-octylsulfanyl-2,2'-bithiophene afforded a symmetric octithiophene able to form homogeneous films, that was characterized through NMR, MS, GPC.

2002 - Complessi di Pt(II) con cisteina S-funzionalizzata [Abstract in Atti di Convegno]
Parenti, Francesca; A., Bellei; Mucci, Adele; Schenetti, Luisa
abstract

Sono riportate le sintesi e le caratterizzazioni di complessi di Pt(II) con cisteina S-funzionalizzata

2002 - Coordination modes of 9-methyladenine in cis-Platinum(II) complexes with dimethylphenylphosphanes as ancillary ligands [Abstract in Atti di Convegno]
B., Longato; Mucci, Adele; Schenetti, Luisa
abstract

The reaction of 9-methyladenine with cis-[L2Pt(NO3)2] in a 2:1 molar ratio, generates a bis-adduct compound that was isolated and fully characterised by 1H, 13C, 31P, 195Pt and 15N NMR spectroscopy.

2002 - Erratum: On the Recovery of 3JH,H and the Reduction of Molecular Symmetry by Simple NMR Inverse Detection Experiments [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Simple 1H,13C correlation spectra obtained by inverse detection techniques provide useful evidence of molecular symmetry. The emblematic case of cis- and trans-stilbenes together with that of a symmetric terthiophene are reported as examples. The effects of a reduction of symmetry on both direct and long-range correlations are reported

2002 - Inverse detection applied to the 1H and 13C assignment and to the regiochemical characterization of beta-substituted alpha,alpha' coupled oligo- and polythiophenes [Capitolo/Saggio]
Schenetti, Luisa; Mucci, Adele
abstract

beta-Substituted alpha-alpha'-coupled oligo- (OTs) and polythiophenes (PTs) are materials currently investigated for their potential applications in optical and electronic devices. beta-Substituents modify both processability and electronic properties with respect to the unsubstituted analogues and these modifications are function not only of the type of substituents but also of their relative positions. When two beta-substituted thiophenes are alpha-alpha' coupled three regiochemically different bithiophenes can be obtained from the three different possible coupling paths: head-to-head, head-to-tail and tail-to-tail. The number of regioisomers enhances in longer oligomers, whereas the interpretation of 1-H and 13-C of PTs is usually based on a four configurational triad model. When the complete 1-H and 13-C assignment and the regiochemical characterisation of OTs and PTs are required, 1-H and 13-C inverse detection proves to be a very powerful tool of investigation. Heteronuclear inverse-detected correlations over one and more bonds are studied and the proton and carbon assignments are often contextual. One-bond correlations are utilised to distinguish between alpha and beta(C,H) pairs, thanks to the different values of alpha and beta 1J(H,C) coupling constantsof thiophene. As far as PTs are concerned, the absence of alpha(C,H) pairs confirms that only alpha,alpha' coupling occurred. Intra-residue correlations over two or three bonds are found running experiments with diffferent evolution delays. When long evolution delays are employed inter-residue correlations are also detected. These last correlations are extremely useful in establishing the thiophene backbone connectivities. Similarly, the association of each beta-substituent to the corresponding ring is found through long-range correlations.

2002 - On the recovery of (3)J(H,H) and the reduction of molecular symmetry by simple NMR inverse detection experiments [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

Simple H-1, C-13 correlation spectra obtained by inverse detection techniques provide useful evidence of molecular symmetry, The emblematic case of cis- and trans-stilbenes together with that of a symnietric terthiophene are reported as examples. The effects of a reduction of symmetry on both direct and long-range correlations are reported.

2002 - Polimeri conduttori coordinati con ioni metallici come nuovi materiali per sensori elettrocatalitici [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Pigani, Laura; M. I., Pilo; P., Piu; G., Sanna; Schenetti, Luisa; Seeber, Renato; N., Spano; Zanardi, Chiara
abstract

v. allegato

2002 - Polythiophene derivative conducting polymer modified electrodes and microelectrodes for determination of ascorbic acid. Effect of possible interferents [Articolo su rivista]
S., Lupu; Mucci, Adele; Pigani, Laura; Seeber, Renato; Zanardi, Chiara
abstract

Conventional-size electrodes and microelectrodes coated by electrogenerated poly[4,4'-bis(butylsulfanyl)-2,2'-bithiophene] have been tested with respect to the electrocatalytic oxidation of a particularly interesting analyte, i.e., ascorbic acid, in different concentrations of phosphate buffer, aqueous solution. Linear sweep and cyclic voltammetry have been used and the quantities related to the analyte concentration were the peak current and the diffusion (t(-1/2)) deconvoluted peak current in the case of conventional-size and of microelectrode, respectively. Fairly good linear correlation could be found; a particularly wide linearity range was obtained by working with the microelectrode. It showed to give good results also at a very low (10(-4) M) phosphate buffer-supporting electrolyte concentration. The actual interference on the analysis of compounds often coupled with ascorbic acid in natural or pharmaceutical products has been studied.

2002 - Sintesi e proprietà di octatiofeni beta-funzionalizzati [Abstract in Atti di Convegno]
A., Bellei; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa
abstract

E' riportato uno studio sulla filmabilità di octitiofeni funzionalizzati con gruppi alchilsulfanilici. Sono stati confrontati diversi sistemi di depisizione (casting, spin coating, Langmuir-Blodgett).

2001 - 4,3'',4''''',4'''''''-Tetrabromo-4',4''',3'''',3''''''-tetra(ottilsulfanil)-2,2':5',2'':5'',2''':5''',2'''':5'''',2''''':5''''',2'''''':5'''''',2'''''''-octatiofene: Sintesi e proprieta' [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Zanardi, Chiara
abstract

E' riportata la sintesi , a partire da un bitiofene asimmetricamente disostituito in 4- e 4'-, di un octatiofene simmetrico sostituito in beta con catene ottilsulfaniliche e atomi di bromo. L'octatiofene, che ha una spiccata tendenza a formare film omogenei, è stato caratterizzato tramite NMR, GPC, UV-Vis.

2001 - Beta-Functionalised alpha,alpha'-conjugated oligothiophenes with alkylsulfanyl groups: synthesis and characterisation [Articolo su rivista]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Zanardi, Chiara
abstract

alpha-oligothiophenes are important materials for optical and electronic devices and are used as model compounds for the characterization of charge carriers in conjugated chains. The presence of beta-alkylsulfanyl groups on the thiophene ring reduces the band-gap between ground and excited state, and influence the electrical and optical properties in a positive manner in relation to possible applications of these materials. the syntheses of a homologous series of alkylsulfanyl oligothiophenes, up to octithiophenes, is discussed

2001 - Bromo- e dibromo-bitiofeni come precursori di bitiofeni beta-funzionalizzati [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Zanardi, Chiara
abstract

Sono riportate le metodologie sintetiche che permettono di partire da bromo- e dibromo-bitiofeni per ottenere bitiofeni beta-funzionalizzati.

2001 - Comparison between Roesy and C-13 NMR complexation shifts in deriving the geometry of inclusion compounds: A study on the interaction between hyodeoxycholic acid and 2-hydroxypropyl-beta-cyclodextrin [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa; Vandelli, Maria Angela; Ruozi, Barbara; Salvioli, Gianfranco; Forni, Flavio
abstract

The formation and geometry of the hyodeoxycholic acid (HDCA)/ 2-hydroxypropyl-beta -cyclodextrin (HP beta CD) complex in methanol-d(4) solution was determined through a rotating frame nuclear Overhauser (ROESY) experiment. The reported results confirmed those independently and previously obtained though the use of C-13 complexation shifts in the same solvent. The C-13 approach, which needs shorter experimental times and is currently used in the study of HP beta CD/bile acid systems, was then substantiated.

2001 - Determinazione dei siti di metallazione di nucleobasi modello in complessi fosfinici di Pt(II) [Abstract in Atti di Convegno]
B., Longato; Mucci, Adele; Schenetti, Luisa
abstract

Sono riportate le strategie di determinazione dei siti di metallazione di nucleobasi modello in complessi fosfinici di Pt(II) basate su esperimenti 1H,15N in inverse detection.

2001 - Electropolymerisation and characterisation of poly[4,4 '-bis(butylsulphanyl)-2,2 '-bithiophene] [Articolo su rivista]
B., Ballarin; F., Costanzo; F., Mori; Mucci, Adele; Pigani, Laura; Schenetti, Luisa; Seeber, Renato; D., Tonelli; Zanardi, Chiara
abstract

Electrochemical properties of electrogenerated poly[4,4'-bis(butylsulphanyl)-2.3'-bithiophene] have been studied. with particular attention to the charge-discharge processes. The possibility of both p- and n-doping is indicated. Doping and relevant de-doping processes of the specific polymer have also been considered in the context of the more general, still un-solved problem of the analysis of the mechanisms that al-e operative in the case of simple polythiophenes. In situ spectroelectrochemical measurements have been used to support the electrochemical results and both in situ UV-visible NIR spectroscopy on neutral, p- and n-doped forms of the polymer, and ex situ IR measurements have been performed. (C) 2001 Elsevier Science Ltd. All rights reserved.

2001 - Evidence of high charge mobility in photoirradiated polythiophene-fullerene composites [Articolo su rivista]
L., Pasimeni; L., Franco; M., Ruzzi; Mucci, Adele; Schenetti, Luisa; C., Luo; Dm, Guldi; K., Kordatos; M., Prato
abstract

Interpenetrating networks of polythiophenes and fullerene derivatives give rise to charge transfer after irradiation with visible light. The resulting radical ion pairs have been studied by time-resolved EPR spectroscopy. At low temperatures (20 K), the radical pairs are spin correlated and locked at a distance of 27.1 Angstrom, whereas an increase of temperature causes the electron and the hole to move further away from each other.

2001 - Intramolecular Diels-Alder cycloaddition of N-allyl-N-(2-furylmethyl)amides - First step of a new route towards the synthesis of a densely functionalized pyrrolizidine ring [Articolo su rivista]
Ghelfi, Franco; Af, Parsons; D., Tommasini; Mucci, Adele
abstract

The intramolecular Diels-Alder reaction of N-allyl-N-(2-furylmethyl)amides to exo-N-acyl-3-aza-10-oxatricyclo[5.2.1.0(1)-,5]dec-8-enes is described. The cycloaddition is controlled not only by the size of the amide appendage, but, also by electronegativity of the amide. An example of a new approach towards the synthesis of a highly functionalized pyrrolizidine ring, which links this Diels-Alder cycloaddition to an halogen atom transfer radical cyclization, is reported.

2001 - Metal-catalised cross coupling of beta-alkylsulfanyl thiophenes [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Zanardi, Chiara
abstract

The synthesis of three isomeric bithiophenes via different coupling reactions was reported.

2001 - Politiofeni funzionalizzati con gruppi alchilsulfanilici [Abstract in Atti di Convegno]
Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Seeber, Renato; Zanardi, Chiara
abstract

v.allegato

2001 - Reactivity of coordinated nitriles - Formation of the acetamidine complex cis-[(PMe3)(2)Pt{1-MeTyH)}{CH3C(NH)NH2}](+) from the 1-methylthyminate compound cis-[(PMe3)(2)Pt{1-MeTyH)}(CH3CN)](+) - Synthesis, characterisation, and X-ray structures [Articolo su rivista]
B., Longato; G., Bandoli; Mucci, Adele; Schenetti, Luisa
abstract

1-Methylthymine (1-MeTy) reacts reversibly with the hydroxo complexes cis-[(PMe3)(2)Pt(mu -OH)](2)X-2 (X- = NO3; ClO4) in various solvents (S = CH3CN, H2O, DMSO) to give the thyminate derivatives cis-[(PMe3)(2)Pt{1-MeTy(-H)}(S)]X that have been isolated as pure compounds when S is CH3CN. The single-crystal X-ray structure of cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)]ClO4 shows that the N(3)-platinated nucleobase acts as a monodentate ligand and a molecule of CH3CN completes the coordination sphere of the metal. Crystals of the acetamidine derivative cis-[(PMe3)(2)Pt{1-MeTy(-H)}{CH3C(NH)NH2}]X were isolated from an acetonitrile solution of this complex, in the presence of small amounts of water, after several months at room temperature, separated in 5-10% yield. The X-ray analysis of the perchlorate salt shows a configuration of the amidine ligand consistent with a formal trans addition of NH3 to the CN triple bond of the coordinated nitrile. The acetamidine complex was formed in high yield (70%), in a few weeks, when aqueous solution of NH3 was added to cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)](+) dissolved in CH3CN. Side products of this reaction are the ammonia complex cis-[(PMe3)(2)Pt{1-MeTy(-H)}(NH3)](+), which was also obtained as pure compound, acetamide, and other platinum containing species. All the isolated complexes were characterised by elemental analysis, IR, and multinuclear NMR spectroscopy.

2001 - Synthesis and Spectroscopic and Electrochemical Characterisation of a Conducting Polythiophene Bearing a Chiral β-Substituent: Polymerisation of (+)-4,4′-Bis[(S)-2-methylbutylsulfanyl]-2,2′-bithiophene [Articolo su rivista]
Iarossi, Dario; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Seeber, Renato; Zanardi, Chiara; Forni, Arrigo; Tonelli, Massimo
abstract

A regioregular head-to-head/tail-to-tail poly(b,b'-disubstituted bithiophene) P1 was synthesised by chemical and electrochemical polymerisation of 2,2'-bithiophene that bears (S)-2-methylbutylsulfanyl chains in the b and b'-positions. The polymer was characterised by GPC, NMR and UV/Vis spectroscopy,CD, AFM and by electrochemical and conductivity measurements.The CD spectra of P1 in solutions in which poor solvents are present show interesting features and allow the presenceof different optically active species to be distinguished. Upon varying the casting conditions of P1, different relativeamounts of grainy and homogeneous aggregated phases were observed in AFM micrographies of films and correspondingnegative or positive first Cotton effects were found in the CD spectra. AFM, CD and UV/Vis characterisations were also performed on an electrogenerated optically active polymerPE1, in order to make a comparison with the chemically synthesised one. The interesting, small band gap of P1 allowsfor easy p- and n-electrochemical doping.

2001 - Unusual access to 5-methoxy or 5,5-dimethoxy-4-methyl-3-pyrrolin-2-ones from chlorinated 4-methyl-pyrrolidin-2-ones [Articolo su rivista]
Bellesia, Franco; L., DE BUYCK; M. V., Colucci; Ghelfi, Franco; I., Laureyn; Libertini, Emanuela; Mucci, Adele; Pagnoni, Ugo Maria; Pinetti, Adriano; T. M., Rogge; C. V., Stevens
abstract

The reaction of N-substituted 4-methyl-2-pyrrolidinones, carrying not less than two chlorine atoms on the C(3) and C(6) carbons afforded with alkaline methoxide in methanol, under mild conditions, the corresponding 5-methoxy or 5,5-dimethoxy-4-methyl-3-pyrrolin-2-ones in satisfactory yields.

2001 - β-Functionalised α,α’-conjugated oligothiophenes with alkylsulfanyl groups: synthesis and characterisation [Capitolo/Saggio]
Mucci, A.; Zanardi, C.; Parenti, F.; Schenetti, L.
abstract

α-Oligothiophenes are important materials for optical and electronic devices and are used as model compounds for the characterisation of charge carriers in conjugated chains. The presence of substituents in β- position of the thiophene ring improves solubility and processability and enables the chemical-physical properties of these materials to be modulate. Among the substituents, the choice of alkylsulfanyl groups is due to the electron donor effect of the sulfur atom which positively reduces the band-gap between ground and excited state, and influences the electrical and optical properties interesting in relation to possible applications of these materials. A synthesis of a homologous series of β-substituted oligothiophenes bearing alkylsulfanyl groups up to octatiophenes is discussed. The alkyl residues of the alkylsulfanyl moieties are methyl-, butyl-, octyl- and (+)-(S)-2-methylbutyl groups. The regiochemistry of all synthesised oligomers is unambiguously assessed by using 1H and 13C NMR spectroscopy. The electrochemical behaviour of some of these derivatives is analysed in relation to their potential applicability in electrochemical devices.

2000 - A solution and solid state study on 2-hydroxypropyl-beta-cyclodextrin complexation with hyodeoxycholic acid [Articolo su rivista]
Vandelli, Maria Angela; Ruozi, Barbara; Forni, Flavio; Mucci, Adele; Salvioli, Gianfranco; Galli, Ermanno
abstract

Hyodeoxycholic acid (HDCA) is a 6-alpha dihydroxylated natural bile acid capable of preventing gallstone formation by reducing the bile cholesterol saturation. However, any attempt to enrich the bile acid pool with HDCA have failed owing to the poor solubility of the molecule. To resolve the bioavailability problems, the complexation of HDCA into the HP beta CD cavity was studied in solution (solubility methods, C-13- and H-1-NMR spectroscopy and circular dichroism) and in the solid state (IR spectroscopy, X-ray diffractometry and thermal analysis). According to the results, the HDCA inclusion took place with 1 : 1 stoichiometry. The influence of different preparation methods of the solid complex was evaluated for its potential use in appropriate pharmaceutical formulations to improve the bioavailability of HDCA.

2000 - Gas sensing measurements and analysis of the optical properties of poly(3-butylthio)thiophene Langmuir-Blodgett films [Articolo su rivista]
R., Rella; P., Siciliano; F., Quaranta; T., Primo; L., Valli; Schenetti, Luisa; Mucci, Adele; Iarossi, Dario
abstract

Films of poly[(3-butylthio)thiophene] were prepared via Langmuir-Blodgett (LB) deposition and casting techniques for applications in gas sensor devices. A description of the preparation of the sensing layer is given for both methods: the LB deposition of the polymer in mixture with arachidic acid and the solvent casting by using directly a solution of the polymer in chloroform. In both cases, alumina substrates equipped with gold interdigitated electrodes have been used. In particular, the samples so prepared show variation in the electrical conductivity when exposed to NO2-oxidising or NH3-reducing agents at a working temperature of about 100 degrees C. The refractive index n and the extinction coefficient ii at normal incidence have been determined in the 400-800 nm spectral range and an energy gap (highest occupied-molecular-orbital or conduction band (HOMO)-lowest unoccupied molecular-orbital or valence band (LUMO) separation) of about 1.9 eV has been estimated.

2000 - H-1 and C-13 nuclear magnetic resonance identification and characterization of components of chondroitin sulfates of various origin [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa; Volpi, Nicola
abstract

Three natural chondroitin sulfates (CSs), from porcine and bovine trachea, and from shark cartilage, were studied using a variety of NMR techniques (DQS, TOCSY, NOESY, HMQC). A good H-1 and C-13 characterization of the major components, chondroitin 4-sulfate (CS4) and chondroitin 6-sulfate (CS6), was obtained and a number of signals coming from chondroitin 2,6-disulfate (CS2,6) (present only in shark CS) was identified. The study of a chemically desulfated CS was necessary in order to understand the difficulties encountered in detecting signals from the chondroitin non-sulfate (CS0) component of porcine and bovine CSs. The singular pattern of UC-4 and NC-1 signals was recognized and explained in terms of a diad model. The excess of multiplicity affecting mainly these two signals was attributed to the differences in the conformation of the N 1:4 U glycosidic bond. Further support to this hypothesis comes from the comparison of the NOESY spectra of the three CSs. (C) 2000 Elsevier Science Ltd. All rights reserved.

2000 - Poli[4,4'-bis(metilbutilsulfanil)-2,2'-bitiofene]: Sintesi e Proprietà [Abstract in Atti di Convegno]
Iarossi, Dario; Mucci, Adele; Parenti, Francesca; Schenetti, Luisa; Zanardi, Chiara; Forni, Arrigo
abstract

Sono riportate la sintesi e la caratterizzazione del poli[4,4'-bis(metilbutilsulfanil)-2,2'-bitiofene.

1999 - Caratterizzazione 1H e 13C e assegnazione della regiochimica di oligotiofeni tramite tecniche NMR eterocorrelate in inverse-detection [Abstract in Atti di Convegno]
Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

The strategies used in the assignment of the regiochemistry of oligothiophenes, through 2D 1H 13C NMR, were illustrated.

1999 - Caratterizzazione di politiofeni con tecniche in "inverse detection" [Abstract in Atti di Convegno]
Mucci, Adele; Schenetti, Luisa
abstract

Sono state spiegate le strategie alla base della caratterizzazione dei politiofeni con tecniche in "inverse detection".

1999 - Evidence of the existence of 2:1 guest-host complexes between diclofenac and cyclodextrins in D2O solutions. A 1H and 13C NMR study on diclofenac/beta-cyclodextrin and diclofenac/2-hydroxypropyl-beta-cyclodextrin systems [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa; Vandelli, Maria Angela; Ruozi, Barbara; Forni, Flavio
abstract

The interaction of diclofenac sodium salt (DCFNa) and two cyclodextrins, beta-cyclodextrin (CD) and 2-hydroxypropyl-beta-cyclodextrin (HPCD), studied in D2O solution with different NMR techniques (1H, 13C NMR, ROESY experiments, NMR titrations), shows the existence of multiple equilibria involving 1:1 and 2:1 guest–host complexes.

1999 - H-1 and C-13 NMR characterization of poly[3-(6-methoxyhexyl)-2,2 '-bithiophene] [Articolo su rivista]
Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; P., COSTA BIZZARRI; C., DELLA CASA; M., Lanzi
abstract

A full H-1 and C-1 NMR study through the use of one- and two-dimensional techniques (HMQC, HMBC, TOCSY and NOE-difference spectroscopy) was carried out on poly[3-(6-methoxyhexyl)-2,2´-bithiophene]. Inter-ring correlations detected in the HMBC spectra proved to be a valuable tool in the assignment of regiochemistry. NMR data can be interpreted on the basis of a four-triad model. Copyright

1999 - Langmuir-Blodgett films of poly[3-(butylthio)thiophene]: optical properties and electrical measurements in controlled atmosphere [Articolo su rivista]
R., Rella; P., Siciliano; G., Toscano; L., Valli; Schenetti, Luisa; Mucci, Adele; Iarossi, Dario
abstract

Experimental results on the gas-sensing properties of polymer thin films are presented. Langmuir-Blodgett films were formed from a 2:1 M mixture of poly[3-(butylthio)thiophene] (PBTT) and arachidic acid. A stable monolayer was prepared at 20 degrees C on the water surface and it was reiteratively transferred onto various substrates by vertical dipping. The visible spectra of the films indicate a HOMO-LUMO separation of around 1.8 eV with an absorption maximum at about 520 nm. Electrical conductivity measurements performed in controlled atmosphere showed large gas sensitivity to electron-acceptor gases such as nitrogen dioxide at a working temperature of the active layer of about 50 degrees C.

1999 - Polymerization and Characterization of 4,4’-bis(alkylsulfanyl)-2,2’-bithiophenes [Articolo su rivista]
Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Seeber, Renato; F., Goldoni; Affronte, Marco; Nava, Filippo
abstract

Regioregular polymers poly[4,4'-bis(butylsulfanyl)-2,2'-bithiophene] (P1)and poly[4,4'-bis(octylsulfanyl)-2,2'-bithiophene] (P2) were prepared from 4,4'-bis(butylsulfanyl)- and 4,4'-bis(octylsulfanyl)-2,2'-bithiophene, by oxidative polymerization with FeCl3, and characterized by 1-H, and 13-C NMR, FT-IR, ad UV-vis spectroscopies, atomic force microscopy (AFM) , electrical conductivity, and cyclic voltammetry measurements. They exhibit weight-average molecular weights of 8 and 70 kDa, respectively, and are both readily soluble in CHCl3, CH2Cl2, CS2, toluene, and THF. P1 has a lamellar structure, and P2 is a flexible and compact film that can be easily processed and manipulated. In the neutral state, they show UV-vis absorption maxima at about 470 nm in CHCL3 solution and exhibit marked solvatochromism and thermochromism. Furthermore, thay can be cast from orange-red solution to form a violet film. The p-doping potentials have been determined, and the possibility of electrogenerating corresponding polymers has been checked. First comparative characterizations of the electrogenerated polymers bave been carried out.

1999 - Sintesi e caratterizzazione di butilsulfanil sexitiofeni [Abstract in Atti di Convegno]
Antolini, Luciano; Borsari, Marco; F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

E' riporata la sintesi, tramite accoppiamento di Stille e accoppiamento ossidativo con cloruro ferrico, di due sexitiofeni funzionalizzati con catene butilsulfaniliche. La regiochimica della sostituzione è stata determinata tramite 1H,13C NMR in inverse detection.

1999 - Spectroscopic comparison between poly[3-(6-methoxyhexyl)thiophene]s with different steric hindrance [Articolo su rivista]
P., Costa Bizzarri; C., Della Casa; M., Lanzi; F., Bertinelli; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

An alternating methoxyhexylthiophene-thiophene copolymer was synthesized from 3-(6-methoxyhexyl)-2,2'-bithiophene and studied chiefly by means of optical absorption and nuclear magnetic resonance spectroscopy. The results were compared with those of the previously obtained poly[3-(6-methoxyhexyl)-2,5-thienylene]. The differences in the UV-Vis spectra of the two polymers in pure solvents, solvent/non-solvent mixtures and in films are discussed on the basis of the microstructure and the steric hindrance along the backbone. NMR spectroscopy revealed copolymer configuration to be regiorandom with a slight prevalence of head-to-head and tail-to-tail junctions. (C) 1999 Elsevier Science S.A. All rights reserved.

1999 - Stability studies of chondroitin sulfate [Articolo su rivista]
Volpi, Nicola; Mucci, Adele; Schenetti, Luisa
abstract

The stability of chondroitin sulfate (CS) was studied under acidic, neutral and basic conditions at 30 and 60 degrees C. CS is remarkably stable under neutral conditions at low temperature, while it degrades at 60 degrees C producing low-molecular-mass fragments and desulfated products. This decomposition process begins at ca. 500-600 h and is consistent with an acid-catalyzed hydrolysis of glycosidic linkages caused by a drop in pH resulting from acidic products. Under basic conditions, a breakdown of glycosidic linkages causes a decrease in molecular mass due to the beta-elimination reaction, confirmed by a strong increase of absorbance at 232 nm and H-1 NMR. Virtually no loss of O-sulfate groups can be detected in the base-treated CS. Under acidic conditions, the molecular mass decreases probably through hydrolysis of polysaccharidic linkages resulting in an increased number of reducing end groups. Litte or no beta-elimination occurs. A loss of O-sulfate groups was detected, producing desulfated derivatives. (C) 1999 Elsevier Science Ltd. All rights reserved.

1999 - Synthesis of beta-butylsulfanyl alpha-oligothiophenes from 3-butylsulfanyl-2,2 '-bithiophene [Articolo su rivista]
Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Sodini, V.
abstract

beta-Butylsulfanyl quater-, sexi-, and octithiophenes were synthesized by oxidative coupling with iron(III) chloride from 3-butylsulfanyl-2,2'-bithiophene. quaterthiophene was also generated through coupling reactions. The nmr characterization of oligomers is reported and discussed.

1999 - Synthesis, Structural Characterization and Electronic Properties of 3,3'''''-Bis(butylsulfanyl)-2,2':5',2'':5'',2''':5''',2'''':5'''',2'''''-sexithiophene [Articolo su rivista]
Antolini, Luciano; Borsari, Marco; F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

Synthesis and NMR, UV-VIS, electrochemical, mobility and X-ray characterization of 3,3'''''-bis(butylsulfanyl)-2,2': 5',2 :5 ,2': 5',2'''': 5'''',2'''''-sexithiophene are reported. This compound combines the promising properties already observed for 3,3''',3'''''-tris(butylsulfanyl)-2,2' : 5',2 : 5:,2''' : 5''''',2'''' : 5'''',2'''''-sexithiophene with a physical state more suitable for its use in field-effect transistors. In particular, the stability of the oxidized forms, the close packing in the solid state together with the mobility and on/off ratio observed make this sexithiophene of potential interest for organic semiconductors.

1998 - 1H and 13C Characterization of Chondroitin Sulphate from Porcine Trachea and Shark Cartilage [Abstract in Atti di Convegno]
Mucci, Adele; Schenetti, Luisa; Volpi, Nicola
abstract

A detailed 1H and 13C NMR spectroscopic study on chondroitin sulphates from porcine trachea and shark cartilage through DQS, TOCSY, NOESY and HMQC is reported.

1998 - 1H and 13C NMR Study on the Interaction between Diclofenac and 2-Hydroxypropyl-beta-Cyclodextrin [Abstract in Atti di Convegno]
Forni, Flavio; Mucci, Adele; Schenetti, Luisa; Vandelli, Maria Angela
abstract

The interaction bertween Diclofenac and 2-Hydroxypropyl-beta-Cyclodextrin were studied through 1H and 13C NMR spectroscopy.

1998 - Characterization of a low-sulfated chondroitin sulfate from the body of Viviparus ater (mollusca gastropoda). Modification of its structure by lead pollution. [Articolo su rivista]
Volpi, Nicola; Mucci, Adele
abstract

A chondroitin sulfate was purified from the body of Viviparus ater (Mollusca gastropoda) and analyzed for molecular mass, constituent disaccharides, and structure by H-1 NMR and H-1 2D NMR. A quite unique glycosaminoglycan species was isolated having a high molecular mass (greater than 45,000) and low charge density, about 0.60, due to the presence of 42% non-sulfated disaccharide, 5% 6-sulfated disaccharide, 48% 4-sulfated disaccharide, and 5% 4,6-disulfated disaccharide. Specimens of Mollusca were also submitted to lead exposure for different times, and the effect on chondroitin sulfate structure was studied. After 96 h treatment a strong decrease in chondroitin sulfate content was observed with a significant modification of its structure producing a more desulfated polymer, in particular in position 4 of the galactosamine unit. Simultaneously, the amount of unsaturated non-sulfated disaccharide increased with an overall decrease of the charge density.

1998 - Crystal structure of head-to-head and tail-to-tail beta,beta '-dibromo-substituted bithiophenes as model compounds for poly(3-bromothiophene) [Articolo su rivista]
Antolini, Luciano; Folli, Ugo; F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

The X-ray structures of 4,4'-dibromo-2,2'-bithiophene 1, 3,3'-dibromo-2,2'-bithiophene 2 and 3,3',5,5'-tetrabromo-2,2'-bithiophene 3 are rweported. The tail-to-tail dimer 1 is found in an anti planar conformation whereas a large distortion is present in the two head-to-head bithiophenes 2 and 3. These bromo derivatives are model compounds for structural studies on poly(3-bromothiophene).

1998 - POLY[3-(BUTYLTHIO)THIOPHENE]LB FILMS FOR GAS SENSING [Relazione in Atti di Convegno]
R., Rella; P., Siciliano; G., Toscano; L., Valli; Schenetti, Luisa; Mucci, Adele; Iarossi, Dario
abstract

Langmuir-Blodgett thin films of poly[(3-butylthio)thiophene] have been deposited and optically characterized. LB films have evidenced a good sensitivuty nd very fast response time to NO2 gas at operating temperature of about 50 °C.

1998 - Preparazione e caratterizzazione del complesso tra acido iodesossicolico e 2-idrossipropil-beta-ciclodestrina [Abstract in Atti di Convegno]
Vandelli, Maria Angela; Panini, Rossana; Mucci, Adele; Schenetti, Luisa; Ruozi, Barbara; Forni, Flavio
abstract

Preparazione e caratterizzazione del complesso tra acido iodesossicolico e 2-idrossipropil-beta-ciclodestrina

1998 - Studio di interazione Melatonina-Adenosina [Abstract in Atti di Convegno]
Vandelli, Maria Angela; Mucci, Adele; Ruozi, Barbara; Forni, Flavio; Galli, Ermanno
abstract

Studio di interazione Melatonina-Adenosina, XVI Simposio A.D.R.I.T.E.L.F.

1998 - Synthesis and Antimuscarinic Activity of Some Ether- and Thioether-Bearing 1,3-dioxolanes and Related Sulfoxides and Sulfones [Articolo su rivista]
L., Malmusi; Franchini, Silvia; Mucci, Adele; Schenetti, Luisa; U., Gulini; G., Marucci; Brasili, Livio
abstract

A series of 1,3-dioxolane-based ligands, bearing ether, thioether and related sulfoxide and sulfone functionalities, were synthsised and tested as potential muscarinic antagonists. The compounds display moderate to low affinity for the three receptor subtypes M1-M3, with some of them showing a significant selectivity for the M1-M3 over the M2 subtype.

1998 - Synthesis and antimuscarinic activity of some N-(4-dimethylaminomethyl-2-phenyl-1,3)dioxolan-2-ylmethyl)lactam methiodides [Articolo su rivista]
L., Malmusi; Franchini, Silvia; Mucci, Adele; P., Angeli; U., Gulini; G., Marucci; Brasili, Livio
abstract

A series of 1,3-dioxolane-based ligands, having a lactam function were synthesized and tested as potential muscarinic antagonists. The compounds display moderate affinity for the three receptor subtypes M1-M3, with significant selectivity for the M1-M3 over the M2 subtype.

1997 - 1H and 13C Characterization of Chondroitin Sulphate from Beef Trachea [Abstract in Atti di Convegno]
Mucci, Adele; Schenetti, Luisa; Volpi, Nicola
abstract

Chondroitin Sulphate from Beef Trachea was characterized through 1H and 13C NMR spectroscopy

1997 - Characterization of a quasi-regiorandom poly[3-(6-methoxyhexyl)-2,2'-bithiophene] [Abstract in Atti di Convegno]
Mucci, Adele; Schenetti, Luisa; P., Costa Bizzarri; C., Della Casa; M., Lanzi
abstract

A quasi-regiorandom poly[3-(6-methoxyhexyl)-2,2'-bithiophene] was characterized through 1D and 2D 1H and 13C NMR spectroscopy.

1997 - Electron structure and geometry of tiophene derivatives [Abstract in Atti di Convegno]
B. G., Zykov; A. I., Fokin; N. L., Asfandiarov; Schenetti, Luisa; Mucci, Adele; Iarossi, Dario
abstract

Photoelectron spectra of three tiophene derivatives have been measured. Quantum chemical calculations (the MNDO method) of electron structure of molecules under investigation have been carried out. The interpretation of ionization energies in the region 7 - 11 eV has been made with the help of calculations of torsion vibrations of substituents. It is shown that in the case of 3-SMe-Thiophene and 3-SBut-Thiophene contributions of plane and out-of-plane substituent conformations are approximately equal. Molecules of 3-SH-Tiophene have predominantly plane conformation.

1997 - One-step synthesis of tris(butylsulfanyl)sexithiophene from 3-butylsulfanyl-2,2'-bithiophene [Articolo su rivista]
F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

FeCl3 converts, in high yield, 3-butylsulfanyl-2, 2'-bithiophene into a tris(butylsulfanyl)sexithiophene, which shows interesting optical properties and forms a stable radical cation and dication.

1997 - Regiochemistry characterization of poly(3-hexanoyloxyethyl-2,5-thienylene) through proton and carbon nuclear magnetic resonance spectroscopy [Articolo su rivista]
F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; P. C., Bizzarri; C., Dellacasa; M., Lanzi
abstract

The poly(3-hexanoyloxyethyl-2,5-thienylene) was studied by means of mono- and bidimensional nuclear magnetic resonance spectroscopy. The regiochemistry of the polymer is assigned on the basis of the C-13 chemical shifts, which are easily obtained through inverse detection experiments, utilizing a triad-based model.

1997 - Synthesis and NMR characterization of 3,4 '-dibutoxy-2,2 '-bithiophene [Articolo su rivista]
F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

3,4'-Dibromo-2,2'-bithiophene was converted, in high yield, into the corresponding dibutoxy derivative. The H-1 and C-13 nmr data are discussed in comparison with those of 3,3'- and 4,4'-dibutoxy-2,2'-bithiophene in relation to regiochemistry.

1997 - Synthesis and characterization of poly[3-(butylthio)thiophene]: a regioregular head-to-tail polymer [Articolo su rivista]
F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; M., Zambianchi
abstract

Poly[3-(butylthio)thiophene] was obtained from 2,5-dibromo-3-(butylthio) thiophene according to the method of Kobayashi. The polymer was characterized as having regioregular head-to-tail(HT) connections with significant extended conjugation length and optical properties, such as solvatochromism and photoluminescence. The polymer is soluble in common organic solvents and can easily form films.

1997 - Synthesis of 3,4'-dibromo-2,2'-bithiophene: A useful intermediate for 3,4'-disubstituted 2,2'-bithiophenes. X-ray molecular structure of 3,4'-dibromo-2,2'-bithiophene [Articolo su rivista]
Antolini, Luciano; Goldoni, F; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

The first synthesis of 3,4'-dibromo-2,2'-bithiophene via metal-catalysed cross-coupling between a metallated and a halogenated thiophene derivative is described. An X-ray crystal structure of 3,4'-dibromo-2,2'-bithiophene is reported, 3,4'-Dibromo-2,2'-bithiophene was converted into corresponding bis(alkylsulfanyl) derivatives through bromine-lithium exchange, followed by reaction with two dialkyl disulfides (Me2S2 or Bu2S2). The H-1 and C-13 NMR data are discussed.

1996 - 13C Chemical Shifts: A Useful Tool for the Regiochemistry Assignment of Poly(3-Hexanoyloxyethyl-2,5-Thienylene) [Abstract in Atti di Convegno]
Mucci, Adele; F., Goldoni; Iarossi, Dario; Schenetti, Luisa; P., Costa Bizzarri; C., Della Casa; M., Lanzi
abstract

The assignment of the regiochemistry of poly(3-hexanoyloxyethyl-2,5-thienylene) on the basis of the 13C chemical shifts of the configurational triads was reported.

1996 - 9-Methyladenine complexes of platinum(II) stabilized by trimethylphosphine: Use of N-15 nuclear magnetic resonance spectroscopy to assign the coordination site [Articolo su rivista]
Schenetti, Luisa; Mucci, Adele; Longato, B.
abstract

The new 9-methyladenine (made) complexes cis-[Pt(PMe(3))(2)(made)(2)][NO3](2) and cis-[{Pt(PMe(3))(2)(made - H)}(2)][NO3](2) have been prepared and characterized. They are formed by treating stoichiometric amounts of the nucleobase with an aqueous solution of cis-[Pt(PMe(3))(2)(NO3)(2)] at autogenous and neutral pH, respectively. A detailed multinuclear (H-1, P-31, Pt-195, C-13 and N-15 at natural abundance) NMR investigation in (CD3)(2)SO indicated that in the mononuclear complex the adenine ligands are N(1)-co-ordinated and that rotation around the metal-nitrogen bonds is slow on the NMR time-scale leading to the presence of two conformers with a relative abundance of ca. 2 : 1. In the dinuclear complex the NH2-deprotonated adenine acts as a bridging ligand through the N(1) and N(6) atoms. The sites of metal binding are clearly evidenced in the N-15 NMR spectra by the remarkable shifts shown by the co-ordinated nitrogens (60 ppm upfield for the endocyclic atom and 25 ppm downfield for the exocyclic one, with respect to the unco-ordinated nucleobase) and their coupling with the P-31 nucleus of the ligand in mutual trans position ((2)J(NP) ca. 60 Hz).

1996 - Alkylthio-substituted oligothiophenes: The influence of the alkyl chain length on the solid-state and solution properties of 4,4'-bis(butylthio)-2,2'-bithiophene [Articolo su rivista]
Antolini, Luciano; Folli, Ugo; F., Goldoni; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

A solid-state (single crystal X-ray, IR, DSC) and solution (H-1 NMR nuclear Overhauser effect (NOE) and longitudinal relaxation times (T-1)) study of 4,4'-bis(butylthio)-2,2'-bithiophene is reported. The two thienyl rings are coplanar and in an anti orientation in the solid state, whereas a low amount of syn form is present in solution. The n-butylthio chain adopts a fully extended, nearly idealized, anti conformation in the crystal, with all the non-H atoms of the whole molecule strictly coplanar, despite the molecular length, but does not show a preferred orientation in solution. The observed changes on passing from the solid to the solution state are indications of the potential solvatochromic and thermochromic properties of beta-butylthio-substituted oligomers and polymers.

1996 - Complexation of bile acids with 2-hydroxypropyl-beta-cyclodextrin: A C-13-NMR study [Articolo su rivista]
Mucci, Adele; Vandelli, Maria Angela; Salvioli, Gianfranco; L., Malmusi; Forni, Flavio; Schenetti, Luisa
abstract

The interaction of chenodeoxycholic acid (3 alpha,7 alpha-dihydroxy-5 beta-cholan-24-oic acid) 1; cholic acid (3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-cholan-24-oic acid) 2, deoxycholic acid (3 alpha,12 alpha-dihydroxy-5 beta-cholan-24-oic acid) 3 and ursodeoxycholic acid (3 alpha,7 beta-dihydroxy-5 beta-cholan-24-oic acid) 4 with 2-hydroxypropyl-beta-cyclodextrin HP beta CD (partially functionalized) is studied by measuring the changes in C-13-NMR chemical shifts induced by complexation in methanol-d(4). The alkyl chain of the bile acids enters the cyclodextrin cavity. The interaction of 1 and 4 with HP beta CD is stronger, in this solvent, with respect that of 2 and 3.

1996 - Identificazione, caratterizzazione e proprietà biologiche di derivati calconici da Glycyrrhiza Glabra L [Articolo su rivista]
Benvenuti, Stefania; F., Severi; Costantino, Luca; Melegari, Michele; Mucci, Adele
abstract

Sono state isolate, purificate e caratterizzate diverse sostanze di natura calconica e ne è stata saggiata l'attività sull'Aldoso Reduttasi.

1996 - Multinuclear NMR spectroscopy structural properties of ofloxacin [Articolo su rivista]
Mucci, Adele; L., Malmusi; Vandelli, Maria Angela; M., Fresta; Schenetti, Luisa
abstract

An accurate 1-H, 13-C and 15-N NMR study on ofloxacin 1 is reported. The conformational properties of the two mobile regions (the benzoxazine and the piperazinyl ring) are studied and discussed. According to the spectroscopic data, the condensed benzoxazine ring shows a conformational consistent with the C-2 atom below the mean molecular plane and the 3-CH3 group in a pseudo-axial position and the piperazinyl group maintains a conformational favourable to N-1' conjugation with the aromatic ring. How multinuclear NMR spectroscopic studies may impact on biological activity and SAR investigations is discussed.

1996 - One- and two-dimensional NMR study of complexation of ursodeoxycholic acid with beta-cyclodextrin [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa; Vandelli, Maria Angela; Forni, Flavio; Ventura, Paolo; Salvioli, Gianfranco
abstract

The interaction of ursodeoxycholic acid (UDCA) with beta-cyclodextrin (beta-CD) is investigated through one and two-dimensional (ROESY) NMR spectroscopy. The relative orientation of host and guest is unequivocally established: the aliphatic side chain of UDCA enters the torus of B-CD on the side of the secondary hydroxy groups.

1996 - Pharmaceutical evaluation of gelatin microspheres cross-linked with d,l-glyceraldehyde. Determinations of residuals of the preparation procedure. [Articolo su rivista]
A., Griffini; Vandelli, Maria Angela; R., Seghizzi; Mucci, Adele; G., Pifferi
abstract

Pharmaceutical evaluation of gelatin microspheres cross-linked with d,l-glyceraldehyde. Determinations of residuals of the preparation procedure.

1996 - Synthesis and description of chalcone-like compounds, inhibitors of aldose reductase [Articolo su rivista]
Severi, F; Costantino, Luca; Benvenuti, Stefania; Vampa, Gabriella; Mucci, Adele
abstract

A series of hydroxy- and hydroxy-methoxychalcones was synthesized and the inhibitory activity and selectivity of the compounds towards bovine lens aldose reductase (AR) were tested. All the compounds display affinity for AR The most active proved to be 1-(2,4-dihydroxyphenyl)-3-(4-hydroxyphenyl)propen-1-one (isoliquiritigenin, IC50 = 7.60 mu M). The selectivity of this compound was also tested, its inhibitory activity being assayed against glutathione reductase and sorbitol dehydrogenase

1996 - Synthesis of 3,3'- and 4,4'-bis(alkylsulfanyl)-2,2'-bithiophenes from the corresponding dibromo derivatives through lithiation [Articolo su rivista]
Folli, Ugo; Goldoni, F; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa
abstract

Both 3,3'- and 4,4'-dibromo-2,2'-bithiophenes, through bromine-lithium exchange with butyllithium followed by reaction with a dialkyl disulfide (Me(2)S(2) or Bu(2)S(2)), have been converted into the corresponding bis(alkylsulfanyl) derivatives.

1996 - Synthesis, NMR spectroscopy study, and antimuscarinic activity of a series of 2-(acyloxymethyl)-1,3-dioxolanes [Articolo su rivista]
L., Malmusi; Mucci, Adele; Schenetti, Luisa; U., Gulini; G., Marucci; Brasili, Livio
abstract

A series of 1,3-dioxolane-based ligands, bearing hydroxymethyl or ester functionalities, was synthesized and tested as potential muscarinic antagonists. The compounds display moderate to low affinity for the three receptor subtypes M(1)-M(3), with some of them showing a significant selectivity for the M(3) subtype. The configurational and conformational properties were studied using NOE experiments and vicinal coupling constants. The LH and C-13 NMR chemical shifts show stereochemically dependent trends. Quantitative analysis of conformer populations showed that the exocyclic CH2N+(CH3)(3) group is prevalently in a pseudo-axial orientation in the cis isomers and in a pseudo-equatorial orientation in the trans isomers. Copyright

1996 - THE INTERACTION OF BILIAR ACIDS WITH 2-HYDROXYPROPYL-CYCLODEXTRIN IN SOLUTION AND IN THE SOLID STATE [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa; Salvioli, Gianfranco; Ventura, Paolo; Vandelli, Maria Angela; Forni, Flavio
abstract

The interaction of two biliar acids (chenodeoxycholic acid and cholic acid) with 2-hydroxypropyl-beta-cyclodextrin (HP beta CD) in solution and in the solid state was studied using different techniques. The formation of an inclusion complex with a 1 : 1 stoichiometry was suggested by the phase solubility studies. Both differential scanning calorimetry and X-ray diffractometry exhibited the amorphous state of the complex. The inclusion of both biliar acids into the HP beta CD cavity was confirmed by the C-13-NMR studies. Cholic acid showed a weaker affinity with respect to chenodeoxycholic acid probably owing to the presence of a hydroxyl group on C(12) (12 alpha) close to the complexation site.

1995 - 1H-13C NMR inverse detection of poly(3-hexylthiophene): characterization of the structural defects [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa
abstract

NMR inverse detection was applied to the study of regiochemistry of a highly head to tail (HT)-regioregular poly(3-hexylthiophene) (PHT). It proved to be a valuable tool in the characterization of polymerization defects not directly revealable or assignable by inspection of the one-dimensional 13-C spectrum. Almost all the 13-C chemical shifts of the four configurational triads of PHT were derived by utilizing the aromatic protons, whereas through the alpha-protons of the aliphatic chain only carbons belonging to HT-HT connections were detected, owing to the high regiospecificity of the PHT under study and to the high multiplicity of aliphatic proton signals. The correctness of the model of the interpretation of PHT structure based on the four trimers of 3-hexylthiophene was confirmed.

1995 - 2-HYDROXYPROPYL-BETA-CYCLODEXTRIN COMPLEXATION WITH URSODEOXYCHOLIC ACID [Articolo su rivista]
Vandelli, Maria Angela; Salvioli, Gianfranco; Mucci, Adele; Panini, R; Malmusi, L; Forni, Flavio
abstract

The complexation in aqueous medium and in the solid phase of ursodeoxycholic acid (UDCA) with a highly soluble cyclodextrin, 2-hydroxypropyl-beta-cyclodextrin, was studied by means of solubility methods, IR and C-13-NMR spectroscopy, X-ray diffractometry and thermal analysis. UDCA inclusion took place with 1:1 stoichiometry. C-13-NMR analysis suggested that the side chain was introduced into the cyclodextrin cavity. The UDCA/cyclodextrin complex showed better dissolution properties than plain drug crystals. Therefore, the complex may be used to improve the delivery and bioavailability of ursodeoxycholic acid.

1995 - A contribution on the complexation of ursodeoxycholic acid with β-cyclodextrin [Relazione in Atti di Convegno]
Mucci, A.; Vandelli, M. A.; Salvioli, G.; Schenetti, L.; Cameroni, R.
abstract

1995 - A contribution to the complexation of ursodeoxycholic acid with beta-cyclodextrin [Abstract in Atti di Convegno]
Mucci, Adele; Vandelli, Maria Angela; Salvioli, Gianfranco; Schenetti, Luisa; Cameroni, Riccardo
abstract

A contribution to the complexation of ursodeoxycholic acid with beta-cyclodextrin is reported

1995 - CONFORMATIONAL AND CONFIGURATIONAL STUDY OF 1,3-DIOXOLANES BY PROTON AND CARBON NMR-SPECTROSCOPY [Articolo su rivista]
Mucci, Adele; Schenetti, Luisa; Brasili, Livio; Malmusi, L.
abstract

The configurational and conformational properties of six 4-trimethylammoniummethyl 2,2-disubstituted 1,3-dioxolanes were studied using NOE experiments and vicinal coupling constants. Selective 1D NOE experiments proved to be effective tools in the configurational assignment of C-2 relative to C-4, The preferred conformation of the dioxolane ring and the exocyclic group at C-4 was obtained by employing vicinal coupling constants and NOE results. The H-1 and C-13 NMR chemical shifts show stereochemically dependent trends, Quantitative analysis of conformer populations was performed using Haasnoot et al's equation. The -N+(CH3)(3) group was found to be synclinal with respect to the heterocyclic 0-3 atom and points outside the ring, When a phenyl group is present at C-2, the 4-CH2N+ - group in a trans relationship to the 2-phenyl ring was found to occur prevalently in a pseudo-axial orientation, whereas it was established to be prevalently pseudo-equatorial when cis with respect to the phenyl ring.

1995 - CRYSTAL AND MOLECULAR-STRUCTURE OF Z- AND E-1,2-DICHLORO-1,2-BIS(2-CHLOROPHENYL)ETHYLENE. AN X-RAY AND NMR STUDY [Articolo su rivista]
Antolini, Luciano; Folli, Ugo; Iarossi, Dario; Mucci, Adele; Sbardellati, S; Taddei, Ferdinando
abstract

The crystal structures of the title compounds were determined by single crystal X-ray diffraction techniques. The molecule of the Z isomer, which crystallizes in the monoclinic space group C2/c with Z = 4 in a cell of dimensions a = 14.891(2), b = 10.780(2), c = 8.769(1) Angstrom, beta = 97.47(2)degrees, V = 1395.7(7) Angstrom(3), has crystallographic twofold symmetry. The E form crystallizes in the orthorhombic space group Pbca with a = 11.730(1), b = 6.932(1), c = 16.841(1) Angstrom, V = 1369.4(2) Angstrom(3), and Z = 4, Its molecules have crystallographically dictated 1 symmetry. In both isomers the phenyl rings are roughly perpendicular to the average ethylene plane. The atoms characterizing this plane show significant deviations from planarity in the Z isomer. Marked bond-angle distortions at the ethene carbons of both structures are observed. The H-1 and C-13 NMR spectra of the compounds were measured and, particularly in the case of the H-1 chemical shifts, fall into two quite separate spectral regions. At low temperature, two conformational isomers, those with different relative orientation of the C-Cl bonds of the phenyl rings, are observed in the spectrum of each compound.

1995 - Complete Assignment of the Aliphatic Chains in Dimers, Trimers and Polymer of 3-Hexylthiophene through 2D-NMR Spectroscopy [Articolo su rivista]
M., Ferrari; Mucci, Adele; Schenetti, Luisa; L., Malmusi
abstract

The 1-H and 13-C signals of the hexyl chains of the title compounds were fully assigned. The regiochemical features of the aliphatic region of proron and carbon spectra were analysed in dimers and trimers.

1995 - Complexation of ursodeoxycholic acid with beta-cyclodextrin: a ROESY study [Abstract in Atti di Convegno]
Mucci, Adele; Vandelli, Maria Angela; Schenetti, Luisa
abstract

A ROESY study on the inclusion compound formed by beta-cyclodextrin and ursodeoxycholic acid is reported.

1995 - Effect of ortho substituents on the internal rotation processes and conformational preferences of 1,2-diaryl-1,1,2,2-tetrachloroethanes: A 1H and 13C NMR variable temperature and x-ray structural study [Articolo su rivista]
Antolini, L.; Folli, U.; Iarossi, D.; Mucci, A.; Sbardellati, S.; Taddei, F.
abstract

The conformational behaviour of 1,2-diaryl-1,1,2,2-tetrachloroethanes, ortho,ortho'-disubstituted with CN (1), F (2) and CO2CH3 (3), and of the mesityl derivative (4), has been studied in solution by variable temperature H-1 and C-13 NMR spectroscopy. The internal rotation processes around the exocyclic C-C and central C-C bonds appear to have similar energy barriers and thus behave differently from the compounds without ortho substituents, studied previously, which have a higher barrier for the interconversion of anti/gauche conformers. At low temperature, compounds 1-3 exist as mixtures of gauche and anti conformers with the former prevailing; compound 4 is almost exclusively in the gauche form. The solid state crystal and molecular structure has been determined for compounds 2 and 3. The molecule of compound 2 has point symmetry ($) over bar 1, which defines perfect staggering around the central C-C bond with the aromatic rings anti. The structure is affected by statistical disorder due to two alternate orientations of the phenyl rings. The crystal structure of compound 3 indicates one asymmetrical molecule in a gauche conformation. Statistical disorder involves both the methoxycarbonyl substituents at the phenyl rings; these latter display almost the same orientation with respect to the C(sp(3)) carbons, in both compounds.

1995 - INTERNAL-ROTATION AROUND SINGLE BONDS AND CONFORMATIONAL PREFERENCES IN HETEROCYCLIC-ANALOGS OF BENZYL METHYL SULFOXIDE STUDIED WITH NMR TECHNIQUES [Articolo su rivista]
Folli, Ugo; Iarossi, Dario; Mucci, Adele; Taddei, Ferdinando
abstract

The conformational equilibrium related to the internal rotation processes occurring in sulphoxides of the type ArCH2SOCH3 (where Ar=2-thienyl, 2-furyl, 2-pyridinyl and (3-methyl)2-pyridinyl rings) were studied with H-1 and C-13 NMR spectroscopy. Proton chemical shifts and long-range coupling constants (n)J(H, H) were obtained from the iterative analysis of the multiplets and were employed, together with C-13 chemical shifts, long-range (n)J(C, H) and relaxation parameters (NOE and non-selective T-1 values) to obtain stereochemical relationships between the protons present in these molecules. Conformational predictions at a qualitative level were also derived from total molecular energies calculated with the semi-empirical AM1/MNDO method as a function of internal coordinates. The different approaches converged to indicate that the heterocyclic rings adopt an average orientation similar to the perpendicular orientation of the phenyl ring in benzyl methyl sulphoxide and, as regards rotation around the CH2-S bond, the prevalent conformer shows that the methyl group is symmetrically oriented with respect to the methylenic protons, The barriers for internal rotation are rather low and the equilibrium between conformers is dependent on the medium properties. Attempts to obtain conformational results were performed for the molecule of omeprazole, an antiulcer drug which contains the ArCH2SO-R moiety (Ar and R are substituted 2-pyridinyl and 2-benzimidazolyl groups, respectively). With respect to the other compounds examined, the orientation of the Ar ring does not significantly differ and the benzimidazole ring seems to prefer an orientation stereochemically equivalent to that of the methyl group.

1995 - Identificazione, caratterizzazione e proprietà biologiche di derivati calconici da GLYCYRRHIZA GLABRA L. [Abstract in Atti di Convegno]
Benvenuti, Stefania; F., Severi; Costantino, Luca; Melegari, Michele; Mucci, Adele
abstract

Sono state isolate, purificate e caratterizzate diverse sostanze di natura calconica e ne è stata saggiata l'attività sull'Aldoso Reduttasi.

1995 - Invertomers at nitrogen in aziridine carboxylates by multinuclear (H-1, C-13, O-17 and N-15) NMR study [Articolo su rivista]
Forni, Arrigo; Moretti, Irene; Mucci, Adele; Prati, Fabio; Schenetti, Luisa
abstract

A configurational and conformational study of N-substituted, N-acetyl and N-sulfonylaziridines carboxylates has been performed by 1H, 13C 17O and 15N NMR spectroscopy. The presence of acetyl and sulfonyl groups on the ring nitrogen atom seems to reduce greatly the configurational stability at nitrogen.

1995 - Synthesis and Characterization of Isomeric alpha,alpha‘-Bithienyls with beta-Methylthio Substituents [Articolo su rivista]
Folli, Ugo; Iarossi, Dario; M., Montorsi; Mucci, Adele; Schenetti, Luisa
abstract

The three isomeric bithienyl 1,2,3, formally related to the dimerization of 3-(methylsulfanyl)thiophene, have been synthsized by the metal-catalysed coupling between a metallated and a halogenated derivative of thiophene of suitable structure. The 1-H and 13-C NMR data are discussed.

1995 - Synthesis and characterization of isomeric α,α′- bithienyls with β-methylsulfanyl substituents [Articolo su rivista]
Folli, U.; Iarossi, D.; Montorsi, M.; Mucci, A.; Schenetti, L.
abstract

The three isomeric bithienyls, 1, 2 and 3, formally related to the dimerization of 3-(methylsulfanyl)-thiophene, have been synthesized by the metal-catalysed coupling between a metallated and a halogenated derivative of thiophene of suitable structure. The 1H and 13C NMR data are discussed.

1995 - Synthesis, characterization and aldose reductase inhibitory of chalcone derivatives [Abstract in Atti di Convegno]
F., Severi; Benvenuti, Stefania; Costantino, Luca; Vampa, Gabriella; Melegari, Michele; Mucci, Adele
abstract

Synthesis, characterization and aldose reductase inhibitory of chalcone derivatives are reported.

1994 - Characterization of Mono- and Polynuclear Platinum(II) Nucleobase Complexes by Multinuclear NMR Spectroscopy [Abstract in Atti di Convegno]
Schenetti, Luisa; Mucci, Adele; G., Trovò; E., Marasciulo; B., Longato
abstract

Mono- and Polynuclear Platinum(II) Complexes with Nucleobase were characterized by Multinuclear NMR Spectroscopy

1994 - Conformational Preferences of 1,2-Diphenyl Derivatives of 1,1,2,2-Tetrachloroethane with Ortho Substituents: a 1H DNMR 1D and 2D Study [Abstract in Atti di Convegno]
Mucci, Adele; S., Sbardellati
abstract

The conformational preferences of 1,2-diphenyl derivatives of 1,1,2,2-tetrachloroethane with ortho substituents were studied through dynamic NMR, carrying out 1D and 2D NMR experiment at variable temperature.

1994 - HMQC and HMBC Experiments: Useful Tools for the Assignment of the Regiochemistry of Poly(3-Hexylthiophene) through the Unambiguous Characterization of Relative Configurational Diads and Triads [Abstract in Atti di Convegno]
Mucci, Adele; Schenetti, Luisa
abstract

HMQC and HMBC inverse-detection experiments were used for the assignment of the regiochemistry of Poly(3-Hexylthiophene), through the unambiguous characterization of relative configurational diads and triads.

1994 - INTERNAL-ROTATION AND CONFORMATIONAL PREFERENCES IN 1,2-DIARYL DERIVATIVES OF 1,1,2,2-TETRACHLOROETHANE - A H-1 DNMR AND X-RAY STRUCTURAL STUDY [Articolo su rivista]
Antolini, Luciano; Folli, Ugo; Mucci, Adele; Sbardellati, S; Taddei, Ferdinando
abstract

The title compounds show in their H-1 NMR spectra recorded at room temperature signals of different line-width characteristic of molecules with slow internal rotation around sterically crowded single bonds. From the DNMR study in [H-2(6)]acetone solution of the 4,4'-(compound 1) and 3,3'-bis(benzoic acid) dimethyl ester (compound 2) and of the 3,3'-bispyridine (compound 3) derivative the dynamic parameters of two internal rotation processes, with different energies of activation. were extracted. The internal rotation process with higher energy barrier (Delta G* = 13-14 kcal mol(-1)) was assigned to the anti reversible arrow gauche conformer interconversion, and that with lower energy barrier (Delta G* = 8-9 kcal mol(-1)) to the rotation of aromatic rings around the C(sp(3))-C(sp(2)) bond in the gauche conformer. The conformer populations measured at low temperature showed that the gauche conformer is the more abundant. The structural features of the conformers of compounds 1-3 were also investigated theoretically at a semi-empirical level with the AM1/MNDO method. The results of these calculations show that the anti conformer is the most stable one, yet the gauche form has higher polarity and this result could explain the increase of the gauche population in polar solvents. For compound 3 calculations were extended to the whole energy hypersurface having as coordinates the angles of rotation around the central C(sp(3))-C(sp(3)) and C(sp(3))-C(sp(2)) bonds. The theoretical free-energies of activation, even if largely underestimated, show that the barriers for the different internal processes follow the order: barrier for rotation around the C(sp(3))-C(sp(3)) bond > barrier for rotation around the C(sp(3))-C(sp(2)) bond in the gauche conformer > barrier for rotation around the C(sp(3))-C(sp(2)) bond in the anti conformer. This order fits the trend of the first two barriers. experimentally determined. For compound 3 and for the 4,4'-bisbenzonitrile (compound 4) derivative, the crystal and molecular structure was obtained from X-ray analysis: the molecules have crystallographically dictated 1 symmetry with perfectly staggered anti conformation. Longer C-Cl bond lengths and smaller Cl-C-Cl bond angles than those present in structurally similar compounds indicate steric crowding around the C(sp(3))-C(sp(3)) bond. Solid state conformations are in excellent agreement with the calculated ground-state rotational structure of these molecules.

1993 - Analisi Conformazionale in Soluzione di 1,2-Diaril Derivati del Tetracloroetano tramite Risonanza Magnetica Nucleare a Temperatura Variabile [Abstract in Atti di Convegno]
Mucci, Adele; S., Sbardellati
abstract

E' presentato uno studio NMR a temperatura variabile condotto su tetracloroetani. Vengono determinate le barriere alla rotazione attorno al legame centrale Csp3-Csp3 e a quelli C-sp3-Csp2.

1993 - Studio Conformazionale di Diadi e Triadi del Poly(3-n-Esiltiofene) [Abstract in Atti di Convegno]
G., Barbarella; M., Zambianchi; Mucci, Adele; Schenetti, Luisa
abstract

E' presentato uno studio conformazionale sulle diadi e le triadi del poly(3-esiltiofene) basato su misure NMR e calcoli teorici.

1991 - CONFORMATIONAL PREFERENCE OF THE METHYLSULFINYL GROUP BONDED TO THE FURAN AND THIOPHENE RINGS - A THEORETICAL APPROACH [Articolo su rivista]
Benassi, Rois; Folli, Ugo; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

The ground state conformations and transition states for conformer interconversion in the two isomers of the of furan (1 and 2) and thiophene (3 and 4) were identified through a theoretical approach based on ab-initio molecular orbital calculations. Two minima and two transition states were found in the potential energy profiles for all the molecules, but the behaviour of 2-methylsulphinyl furan (1) differs somewhat from that of the other compounds. The minima correspond to the two orientations of the S-O bond with respect to the heterocyclic heteroatom X (X = O or S), labelled X,O-cis an X,O-trans. The conformer having the S-O bond oriented s-cis with respect to the internal double bond with higher pi density (X,O-cis for the 3-methylsulphinyl derivatives and X,O-trans for the 2-methylsulphinyl derivatives) has a twist angle phi (between the S-O bond and the heterocyclic ring) of a few degrees. Larger distortions are present in the conformers with opposite orientation of the S-O bond, and the twist angle has the highest value (phi = 62.8-degrees) in compound 1. The transition states correspond to the methyl group being nearly coplanar with the heterocyclic ring and this situation seems to be due mostly to a loss of pi electron delocalization. More complex is the transition state situation for compound 1, since a barrier in the potential energy for internal rotation is imposed also by the repulsion between the heterocyclic and sulphinyl oxygen atoms. The conformer populations were estimated from the potential energy

1991 - CRYSTAL AND MOLECULAR-STRUCTURE OF METHYLSULFINYL DERIVATIVES OF FURAN AND THIOPHENE BY X-RAY-DIFFRACTION [Articolo su rivista]
Folli, Ugo; Iarossi, Dario; Mucci, Adele; Musatti, A; Nardelli, M; Schenetti, Luisa; Taddei, Ferdinando
abstract

An investigation of the solid-state conformational properties of 3-methylsulphinyl derivatives of furan and 2- and 3-methylsulphinyl derivatives of thiophene, which also contain halogen atoms in the heterocyclic ring, is reported. For 3-iodo-2-(methylsulphinyl)thiophene, compound 1, two crystallographically independent molecules were found in the unit cell, and in 2-bromo-4-iodo-3-(methylsulphinyl)thiophene, compound 5, a high degree of disorder is present. The sulphur atom of the methylsulphinyl group has a pyramidal structure. The methyl group is highly twisted with respect to the ring plane and the S-O bond adopts different orientations in the molecules examined. When only one halogen atom is present in the ring the S-O bond is directed to the opposite side of the ring with respect to this atom, yet the relative position of the substituents determines a different twist of this bond with respect to the heterocyclic plane.

1991 - Conformational analysis of methylsulphinyl derivatives of furan and thiophene by employing nuclear magnetic relaxation and lanthanide induced shifts [Articolo su rivista]
Folli, Ugo; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

Relaxation parameters such as nuclear Overhauser effect (NOE) and spin-lattice relaxation times (T1) were applied to the conformational analysis of methylsulphinyl derivatives of furan and thiophene. Correlation times for molecular tumbling tau-c, and for methyl reorientation, tau-i, were obtained. The tau-i values for the different molecules examined are nearly the same, the tau-c are twice as large in derivatives that also contain an iodine substituent in the heterocyclic ring. From non-selective, selective and bi-selective T1 measurements and NOE values, relative to H-1 nuclei, and a best-fit procedure, the most probable conformational intervals for the methylsulphinyl group were located. Owing to the pyramidal structure of sulphoxides, the preferred conformers could not be fixed unambiguously. From the Lanthanide Induced Shift (LIS) technique on H-1 and C-13 nuclei, intervals of preferred orientations of the S-O bond with respect to the heterocyclic ring were found. Reliable conclusions about the conformational behaviour of these molecules have been drawn by matching the two sets of results. Relaxation parameters turn out to be useful for conformational analysis of small molecules when employed as a complementary tool with other experimental approaches.

1991 - PREFERRED ORIENTATIONS OF THE S-O BOND IN METHYLSULFINYL DERIVATIVES OF FURAN AND THIOPHENE - AN EXPERIMENTAL-STUDY BASED ON H-1, C-13, AND O-17 NMR-SPECTROSCOPY [Articolo su rivista]
Benassi, Rois; Folli, Ugo; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

The preferred conformations of the methylsulphinyl group bonded to the heterocycles furan and thiophene have been studied with NMR techniques in solution. The presence of one halogen atom ortho to the methylsulphinyl group determines the orientation of the S-O bond in the opposite direction with respect to the halogen, and the degree of coplanarity of this bond with the ring depends on the substitution-pattern. The higher degree of coplanarity is found when the methylsulphinyl group and the halogen substituent are in position 3 and 4. Two ortho substituents determine structures with large twists of the methylsulphinyl group. The chemical shifts of H-1, C-13 and O-17 nuclei of the methylsulphinyl group and referred to spectra in solution do not evidence trends of general validity for all the compounds examined as a function of the orientation of the methylsulphinyl group with respect to the ring. Such trends were present in the case of the corresponding phenyl derivatives. Nevertheless, by examining the behaviour of long-range (n)J(C,H) coupling constants, involving the carbon nucleus of the methyl group, together with chemical shifts, conclusions regarding the conformational behaviour of these molecules in solution can be derived. Possible perturbations of the equilibrium caused by the polarity of the medium are evidenced as well. The results indicate that in the 2-methylsulphinyl

1990 - CONFORMATIONAL ANALYSIS OF METHYL PHENYL SULFOXIDES CONTAINING FLUORINE SUBSTITUENTS IN THE PHENYL RING BASED ON H-1, C-13 AND O-17 NMR CHEMICAL SHIFTS AND LONG-RANGE nJ(HF) AND n(CF) COUPLING CONSTANTS [Articolo su rivista]
Benassi, Rois; Folli, Ugo; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

A conformational study on methyl phanyl sulphoxides, carrying different subtituents on the phenyl rings, based on the interpretation of H-1, C-13 AND O-17 NMR chemical shifts and long range J(H,F) and J(C,F) coupling constants is reported

1989 - Conformational Study of Substituted Methyl Phenyl Sulphoxides. A Multinuclear (1H, 13C and 17O) Approach., J. Chem. Soc. Perkin Trans. 2, [Articolo su rivista]
Benassi, Rois; Folli, Ugo; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

A number of ring-substituted methyl phenyl sulphoxides have been examined with a multinuclear n.m.r. approach in order to obtain experimental evidence of the conformational properties of the methylsulphinyl group bonded to an aromatic ring. Measurements were performed of 1H, 13C, and 17O chemical shifts and LIS (lanthanide-induced shifts) on 1H and 13C, long-range 13C–1H coupling constants. Each of these approaches by itself is not fully conclusive in showing the orientation of the SO bond in the different compounds examined, but by using them in combination a sound picture of the conformational behaviour of these molecules in solution can be obtained. The SO bond is thus almost coplanar with the aromatic ring in ortho-substituted compounds and oriented in the opposite direction with respect to the substituent. The twist-angle probably differs slightly as a function of the ortho-group. An increasing degree of distortion from coplanarity is found in para-substituted derivatives and ortho-disubstituted compounds. As regards 17O chemical shifts, these were found to span a smaller range than in the corresponding acetophenones.

1989 - Conformational preference in methyl phenyl sulphoxide and in ortho substituted fluorine derivatives: a theoretical approach [Articolo su rivista]
Benassi, Rois; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

Ab initio MO calculations (3-21G*//3-lG* basis set) have been performed for methylphenyl sulphoxide ( 1) ,2-fluoro- (2 ) and 2,6-difluoro- (3 ) derivatives in order to examine the structuralproperties of their conformational ground state (8). The conformational energy profile for rotation around the C,,-S bond has been constructed in the STO-3G* basis set and the minima have been located at the 3-21G* level allowing relaxation of the geometrical parameters of the methylsulphinyl group. For methylphenyl sulphoxide one energy minimum is found and corresponds to the SO bond nearly eclipsed with the phenyl ring (twist angle 7.31” ). Two energy minima are found for compound 2 and in the more stable conformation the SO bond is coplanar with the ring and anti with respect to the ortho fluorine substituent. In the less stable ground state the lone pair of the sulphur atom settles in the nodal plane of the n-electron cloud of the phenyl ring. This conformation is structurally close to the conformational ground state of compound 3. For compound1 the properties of the transition state have also been determined at the 3-21G* level. The energy barrier for internal rotation corresponds to the S-C bond of the methyl sulphinyl group eclipsed with one ortho C-H bond. The origin of the conformational ground- and transition-states in thesemolecules is discussed on the basis of their electronic structure.

1989 - Conformational study of substituted methyl phenyl sulphoxides. A multinuclear (1H, 13C, and 17O) approach [Articolo su rivista]
Benassi, R.; Folli, U.; Iarossi, D.; Mucci, A.; Schenetti, L.; Taddei, F.
abstract

A number of ring-substituted methyl phenyl sulphoxides have been examined with a multinuclear n.m.r. approach in order to obtain experimental evidence of the conformational properties of the methylsulphinyl group bonded to an aromatic ring. Measurements were performed of 1H, 13C, and 17O chemical shifts and LIS (lanthanide-induced shifts) on 1H and 13C, long-range 13C 1H coupling constants. Each of these approaches by itself is not fully conclusive in showing the orientation of the SO bond in the different compounds examined, but by using them in combination a sound picture of the conformational behaviour of these molecules in solution can be obtained. The SO bond is thus almost coplanar with the aromatic ring in ortho-substituted compounds and oriented in the opposite direction with respect to the substituent. The twist-angle probably differs slightly as a function of the ortho-group. An increasing degree of distortion from coplanarity is found in parasubstituted derivatives and ortho-disubstituted compounds. As regards 170 chemical shifts, these were found to span a smaller range than in the corresponding acetophenones.

1988 - L’equilibrio conformazionale del gruppo metilsolfinilico legato ad anelli aromatici ed eteroaromatici [Articolo su rivista]
Benassi, Rois; Folli, Ugo; Iarossi, Dario; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

L’equilibrio conformazionale del gruppo metilsolfinilico legato ad anelli aromatici ed eteroaromatici è stato studiato tramite risonanza magnetica nucleare e metodi teorici.

1987 - Costanti di accoppiamento a lungo raggio 13C-1H nell’analisi conformazionale di 3-formil derivati del furano e del tiofene [Abstract in Atti di Convegno]
Benassi, Rois; Folli, Ugo; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

Le costanti di accoppiamento13C-1H a lungo raggio sono state utilizzate nell’analisi conformazionale di 3-formil derivati del furano e del tiofene.

1987 - Long-range 13C-1H Spin-Spin Coupling Constants in the Conformational Analysis of Formil Derivatives of Furan and Thiophene, Magn. Reson. Chem., 25, 804-810 [Articolo su rivista]
Benassi, Rois; Folli, Ugo; Mucci, Adele; Schenetti, Luisa; Taddei, Ferdinando
abstract

The long-range 13C-1H Constants were employed in the conformational analysis of formil derivatives of furan and thiophene