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Cecilia BARALDI
Ricercatore Universitario
Dipartimento Scienze della Vita sede ex Scienze Farmaceutiche Via Campi 103
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Pubblicazioni
2023
- New Lidocaine-Based Pharmaceutical Cocrystals: Preparation, Characterization, and Influence of the Racemic vs. Enantiopure Coformer on the Physico-Chemical Properties
[Articolo su rivista]
Ma, P.; Toussaint, B.; Roberti, E. A.; Scornet, N.; Santos Silva, A.; Castillo Henríquez, L.; Cadasse, M.; Négrier, P.; Massip, S.; Dufat, H.; Hammad, K.; Baraldi, C.; Gamberini, M. C.; Richard, C.; Veesler, S.; Espeau, P.; Lee, T.; Corvis, Y.
abstract
This study describes the preparation, characterization, and influence of the enantiopure vs. racemic coformer on the physico-chemical properties of a pharmaceutical cocrystal. For that purpose, two new 1:1 cocrystals, namely lidocaine:dl-menthol and lidocaine:d-menthol, were prepared. The menthol racemate-based cocrystal was evaluated by means of X-ray diffraction, infrared spectroscopy, Raman, thermal analysis, and solubility experiments. The results were exhaustively compared with the first menthol-based pharmaceutical cocrystal, i.e., lidocaine:l-menthol, discovered in our group 12 years ago. Furthermore, the stable lidocaine/dl-menthol phase diagram has been screened, thoroughly evaluated, and compared to the enantiopure phase diagram. Thus, it has been proven that the racemic vs. enantiopure coformer leads to increased solubility and improved dissolution of lidocaine due to the low stable form induced by menthol molecular disorder in the lidocaine:dl-menthol cocrystal. To date, the 1:1 lidocaine:dl-menthol cocrystal is the third menthol-based pharmaceutical cocrystal, after the 1:1 lidocaine:l-menthol and the 1:2 lopinavir:l-menthol cocrystals reported in 2010 and 2022, respectively. Overall, this study shows promising potential for designing new materials with both improved characteristics and functional properties in the fields of pharmaceutical sciences and crystal engineering.
2022
- Neonatal septic shock, a focus on first line interventions
[Articolo su rivista]
Spaggiari, Valentina; Passini, Erica; Crestani, Sara; Roversi, Maria Federica; Bedetti, Luca; Rossi, Katia; Lucaccioni, Laura; Baraldi, Cecilia; Della Casa Muttini, Elisa; Lugli, Licia; Iughetti, Lorenzo; Berardi, Alberto
abstract
Septic shock is a main cause of morbidity and mortality in neonates. Septic shock evolves from compensated to uncompensated through 3 distinct phases. Prompt diagnosis is challenging, since neonatal septic shock may overlap with the physiological changes occurring at birth. The outcome of septic shock depends on a prompt recognition of symptoms and a strict adherence to cardiopulmonary resuscitation guidelines. Fluid administration plays a major role in the initial management of septic shock. If there is no response to volume filling, inotropes must be infused within one hour of onset (dopamine, dobutamine, adrenaline). Life-threatening infections require immediate and aggressive empiric use of antimicrobials. In the pediatric age, delay in antibiotic initiation for treating septic shock is associated with poor outcome and increased risk of mortality. There is a gap regarding first line interventions in neonatal septic shock. This review addresses initial interventions in the treatment of neonatal septic shock and discusses currently available evidences., These interventions may allow to improve the outcome if they are promptly carried out.
2022
- Spectroscopic investigations, concentration dependent SERS, and molecular docking studies of a hydroxybenzylidene derivative
[Articolo su rivista]
Kumar, V. S.; Mary, Y. S.; Mary, Y. S.; Kratky, M.; Vinsova, J.; Baraldi, C.; Roxy, M. S.; Gamberini, M. C.
abstract
Spectroscopic analysis, density functional theory (DFT) studies and surface enhanced Raman scattering (SERS) of (E)-N’-(5-chloro-2-hydroxybenzylidene)-4-trifluoromethyl) benzohydrazide (CHTB) have been studied on different silver colloids in order to know the particular chemical species responsible for the spectra. Very significant shifts are observed for Raman and SERS wavenumbers. Observed changes in the υ-ring modes may be due to surface interaction of the π-electrons and the presence of this suggested that RingII is more tilted in both cases than RingI and the molecule assumes a tilted orientation for the concentration 10−3 M. Orientation changes are seen in concentration dependent SERS spectra. The molecular electrostatic potential has also been constructed to determine the electron rich and poor site of CHTB. The molecular docking studies indicate that the binding affinity and hydrogen bond interactions with the receptors may be supporting evidence for further studies in designing other pharmaceutical applications of CHTB. Communicated by Ramaswamy H. Sarma.
2021
- Concentration and solvent dependent SERS, DFT, MD simulations and molecular docking studies of a thioxothiazolidine derivative with antimicrobial properties
[Articolo su rivista]
Mary, Y. S.; Mary, Y. S.; Armakovic, S.; Armakovic, S. J.; Kratky, M.; Vinsova, J.; Baraldi, C.; Gamberini, M. C.
abstract
Spectroscopic analysis, DFT studies and surface enhanced Raman scattering of antimicrobial bioactive (Z)-2-[5-(5-bromo-2-hydroxybenzylidene)-4-oxo-2-thioxothiazolidin-3-yl]acetic acid (BPTA) have been studied on different silver sols. Very large changes are observed for Raman and SERS bands. Observed variations in the ring modes may be due to surface π-electron interactions and presence of this indicated that molecule is inclined with respect to the metal surface. Changes in orientation are seen in SERS spectra depending on concentration. The molecular docking results show that binding affinity and interactions with the receptors may be supporting evidence for further studies in design further BPTA pharmaceutical applications. Reactivity properties are obtained from DFT and MD simulations. The quantum-mechanical level of theory has been applied to obtain information about the MEP and ALIE surfaces. These calculations give sensitivity of BPTA towards autoxidation mechanism. An influence of water has been studied computationally, via the MD simulations and RDF analysis. This level of theory was also used to identify possible excipient substance for this molecule.
2021
- Concentration dependent SERS, DFT and molecular docking studies of a ureido derivative with antitubercular properties
[Articolo su rivista]
Mary, Y. S.; Mary, Y. S.; Kratky, M.; Vinsova, J.; Baraldi, C.; Gamberini, M. C.
abstract
Spectroscopic analysis, density functional theory (DFT) studies and surface enhanced Raman scattering (SERS) of antimycobactetial 4-[3-(4-acetylphenyl)ureido]-2-hydroxybenzoic acid (AUHB) have been studied on different silver sols. For Raman and SERS wavenumbers, very large changes are observed. Observed variations in the modes of ring may be due to surface π-electron interactions and presence of this indicated that poly substituted ring is more inclined than para substituted phenyl ring and assumes a inclined position for concentration 10−3 M. Changes in orientation are seen in SERS spectra depending on concentration. In order to find electron-rich and poor sites of AUHB, molecular electrostatic potential was also constructed. The molecular docking results show that binding affinity and interactions with the receptor DprE1 may be supporting evidence for further studies in design further AUHB pharmaceutical applications. Based on antitubercular activity of 4-aminosalicylic acid (PAS) and urea derivatives we designed, synthesized and investigated mutual PAS-urea derivatives as potential antimycobacterial agents.
2021
- DFT, SERS-concentration and solvent dependent and docking studies of a bioactive benzenesulfonamide derivative
[Articolo su rivista]
Sheena Mary, Y.; Shyma Mary, Y.; Kratky, M.; Vinsova, J.; Baraldi, C.; Gamberini, M. C.
abstract
Spectroscopic analysis, DFT studies and surface enhanced Raman scattering (SERS) of antimicrobial bioactive 4-[(5-tert-butyl)2-hydroxybenzylidene]amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (THPB) have been studied on different silver sols. Intensity and hence enhancement variations are observed for Raman and SERS bands. Observed changes in the ring modes may be due to surface π-electron interactions and presence of this indicated that molecule is inclined with respect to the metal surface. Changes in orientation are seen in SERS spectra depending on concentration. The molecular docking results show that binding affinity and interactions with the receptors may be supporting evidence for further studies in design further THPB pharmaceutical applications. Reactivity properties are obtained from DFT analysis.
2021
- DFT, molecular docking and SERS (concentration and solvent dependant) investigations of a methylisoxazole derivative with potential antimicrobial activity
[Articolo su rivista]
Sheena Mary, Y.; Shyma Mary, Y.; Kratky, M.; Vinsova, J.; Baraldi, C.; Gamberini, M. C.
abstract
Spectroscopic analysis, DFT studies and surface enhanced Raman scattering of antimicrobial bioactive 4-[(2‑hydroxy-3,5-diiodobenzylidene)amino]-N-(5-methylisoxazole-3-yl)benzenesulfonamide (HDMB) have been studied. Changes in intensity and enhancement variations are observed for Raman and SERS bands. Changes observed in the ring mode vibrations may be due to surface π-electron interactions which means molecule is orientated in a tilted position with respect to metal surface. Changes in orientation are seen in SERS spectra depending on concentration. The molecular docking results show that binding affinity and interactions with the receptors may be supporting evidence for further studies in design further HDMB pharmaceutical applications. Reactivity properties are obtained from DFT analysis.
2021
- Spectroscopic investigations, concentration dependent SERS, and molecular docking studies of a benzoic acid derivative
[Articolo su rivista]
Gamberini, M. C.; Mary, Y. S.; Mary, Y. S.; Kratky, M.; Vinsova, J.; Baraldi, C.
abstract
Spectroscopic analysis, density functional theory (DFT) studies and surface enhanced Raman scattering of 4-((3-bromo-5-chloro-2-hydroxybenzylidene)amino)benzoic acid (BCHB) have been studied on different silver colloids concentrations in order to know the particular chemical species responsible for the spectra. For Raman and surface enhanced Raman scattering (SERS) wavenumbers, changes are observed. Observed variations in the modes of ring may be due to interaction of the π-electrons and presence of this indicated that RingII is more inclined than RingI and the BCHB assumes inclined orientation for concentration 10-3 M. Changes in orientation are seen in SERS spectra depending on concentration. In order to determine the electron-rich and poor sites of BCHB, the molecular electrostatic potential was also constructed. The molecular docking studies show that the bindings and interactions with the receptors may be supporting evidence for further studies in design further BCHB pharmaceutical applications.
2020
- Investigating Novel Syntheses of a Series of Unique Hybrid PLGA-Chitosan Polymers for Potential Therapeutic Delivery Applications
[Articolo su rivista]
Duskey, Jason Thomas; Baraldi, Cecilia; Gamberini, Maria Cristina; Ottonelli, Ilaria; Da Ros, Federica; Tosi, Giovanni; Forni, Flavio; Vandelli, Maria Angela; Ruozi, Barbara
abstract
Discovering new materials to aid in the therapeutic delivery of drugs is in high demand. PLGA, a FDA approved polymer, is well known in the literature to form films or nanoparticles that can load, protect, and deliver drug molecules; however, its incompatibility with certain drugs (due to hydrophilicity or charge repulsion interactions) limits its use. Combining PLGA or other polymers such as polycaprolactone with other safe and positively-charged molecules, such as chitosan, has been sought after to make hybrid systems that are more flexible in terms of loading ability, but often the reactions for polymer coupling use harsh conditions, films, unpurified products, or create a single unoptimized product. In this work, we aimed to investigate possible innovative improvements regarding two synthetic procedures. Two methods were attempted and analytically compared using nuclear magnetic resonance (NMR), fourier-transform infrared spectroscopy (FT-IR), and dynamic scanning calorimetry (DSC) to furnish pure, homogenous, and tunable PLGA-chitosan hybrid polymers. These were fully characterized by analytical methods. A series of hybrids was produced that could be used to increase the suitability of PLGA with previously non-compatible drug molecules
2020
- Phoenicians Preferred Red Pigments: Chemical Compositions of Make-Up Powders Found in Archaeological Sites from Sicily
[Articolo su rivista]
Baraldi, C.; Toti, M. P.; Van Elslande, E.; Walter, P.; Gamberini, M. C.
abstract
Little is known concerning Phoenician and Punic cosmetics, and pertinent studies and analyses on archaeological finds are particularly scanty. The present study has taken into account 22 archaeological red and pink Punic make-up samples collected in several Sicilian museums. The samples were analyzed by infrared spectroscopy, Raman microscopy, and surface-enhanced Raman spectroscopy (SERS). The analyses revealed an interesting and unusual variability in the use of raw materials, ranging from the mineral to the organic world. Not only traditional dye-based pigments were identified, but also rare ones never reported previously for this use. We show also an occurrence unusual in antiquity of a lead chromate block presumably intended to be ground just before its use in cosmetics.
2020
- Red horse-chestnut of Aesculus X Carnea : a new way for health and food design?
[Capitolo/Saggio]
Baraldi, Cecilia; Foca, Giorgia; Maletti, Laura; Marchetti, Andrea; Roncaglia, Fabrizio; Sighinolfi, Simona; Tassi, Lorenzo
abstract
Some investigations have been performed about the composition of Aesculus X carnea seeds (Red horse-chestnuts). Different experimental techniques have been used to gain more information on morphological structure and proximate chemical composition of this product. Surface analysis by SEM showed internal typical structure of globular-form bodies, containing starch, lipids, proteins, mineral components and many others species, confined in cell walls and cemented by a gelled hydrocolloid. The most representative data related to the chemical composition of naturally desiccated specimen are as follows: proteins 3.16%; lipids 4.34%; total glucides 15.6%. Obviously, this chemical faces modulate some other undifferentiated chemical parameters, such as Cold Water Solubility (CWS = 53.9%), and Total Inorganic Soluble Salts (TISS = 2.79%). A stringent comparison of the present findings has been made with our previous results obtained by working with the seeds of two Hippocastanaceae parent cultivars.
2019
- Archeometria della pittura parietale a Reggio Emilia: gli intonaci dipinti dello scavo di Palazzo Mogardini
[Poster]
Capurso, Annalisa; Baraldi, Pietro; Zannini, Paolo; Baraldi, Cecilia; Lugli, Stefano; Tirelli, Giulia; Rossi, Andrea
abstract
A Reggio Emilia, durante lo scavo di un cortile di Palazzo Mongardini nel 2009, è stato rinvenuto un gruppo di circa 500 frammenti di intonaco dipinto di epoca romana sui quali, dal 2017, è stato intrapreso uno studio da parte di una équipe multidisciplinare. lacerti pittorici, per quanto in giacitura secondaria, appaiono di grande interesse sia in relazione al luogo di ritrovamento, sia per la tecnica di esecuzione. Le indagini XRF, Raman e IR-ATR hanno mostrato che la tavolozza dei pigmenti impiegata è ampia e fa uso di pigmenti stesi con latte di calce a formare uno strato di colore ad affresco. Ma anche la tecnica a mezzo fresco risulta applicata, come nel caso di ripresa di colori dopo la carbonatazione per coprire una stesura o per avere determinati effetti coloristici.
2019
- Characterisation of fibrous ferrierite in the rhyolitic tuffs at Lovelock, Nevada, USA
[Articolo su rivista]
Zoboli, A.; Di Giuseppe, D.; Baraldi, C.; Gamberini, M. C.; Malferrari, D.; Urso, G.; Lassinantti Gualtieri, M.; Bailey, M.; Gualtieri, A. F.
abstract
Ferrierite is the name for a series of zeolite-group of minerals which includes three species with the same ferrierite framework (FER) crystal structure but different extra-framework cations. Recent studies have shown that ferrierite can exhibit a fibrous-asbestiform crystal habit and may possess the same properties as carcinogenic fibrous erionite. Characterisation of the ferrierite in and around a mine location will be helpful in assessing the potential for toxic outcomes of exposure in the mine and any local population.The zeolite-rich tuff deposit of Lovelock, Nevada, USA is the largest occurrence of diagenetic ferrierite-Mg. A previous survey reported that ferrierite hosted in these rocks displays a fibrous morphology. However, these observations concerned a limited number of samples and until now there has been little evidence of widespread occurrence of fibrous ferrierite in the Lovelock deposit.The main goal of this study was to perform a mineralogical and morphometric characterisation of the tuff deposit at Lovelock and evaluate the distribution of fibrous ferrierite in the outcrop. For this purpose, a multi-analytical approach including powder X-ray diffraction, scanning and transmission microscopies, micro-Raman spectroscopy, thermal analyses, and surface-area determination was applied.The results prove fibrous ferrierite is widespread and intermixed with mordenite and orthoclase, although there are variations in the spatial distribution in the bedrock. The crystal habit of the ferrierite ranges from prismatic to asbestiform (elongated, thin and slightly flexible) and fibres are aggregated in bundles. According to the WHO counting criteria, most of the ferrierite fibres can be classified as breathable. While waiting for confirmatory in vitro and in vivo tests to assess the actual toxicity/pathogenicity potential of this mineral fibre, it is recommended to adopt a precautionary approach for mining operations in this area to reduce the risk of exposure.
2019
- DA PLACENTIA AD ARIMINUM: TECNICHE E MATERIALI DELLA PITTURA MURALE ROMANA
NELLE DOMUS DELLA OCTAVA REGIO
Pitture frammentarie di epoca romana da Roma e dal Lazio: nuove ricerche
[Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; Ferrari, Giorgia; Tassi, Lorenzo; Zannini, Paolo
abstract
The analyses of polychrome plaster from the Octava Regio of ancient Roman Italy have enabled the identification
of the palette of pigments used, the pictorial techniques and the different ways of decorating painted
surfaces. Despite the short distances between the towns founded along the Via Aemilia, the paintings exhibit
differences relating to these important domus: the decorative motifs, pigments, intonachinos and plaster all
vary. Some of the more unusual pigments may come from geological features found in the territory or from
the nearby mountains.
2019
- Investigation of the pigment use in the Tomb of the Reliefs and other tombs in the Etruscan Banditaccia Necropolis
[Articolo su rivista]
Alfeld, Matthias; Baraldi, Cecilia; Gamberini, Maria Cristina; Walter, Philippe
abstract
The pigment use in the Tomb of the Reliefs (4th century BC) and four other tombs (7th-4th century BC) in the Etruscan Banditaccia Necropolis near Cerveteri, Italy, has been investigated. We made use of XRF and Raman spot analysis, XRF imaging, IR luminescence and photography supported by Dstretch contrast enhancement. We identified the use of haematite, goethite, calcite, carbon black, manganese oxide, Tyrian purple and Egyptian blue, with the last three only found under the central burial place of the Tomb of the Reliefs. The tuff in which these tombs were cut proved to be a significant challenge for XRF analysis as the signals of Ca, Mn and Fe vary strongly due to the heterogeneity of the stone, so that it is difficult to distinguish between signals from the tuff and the pigments. Finally, we show that lightweight instruments transported in check-in luggage may not answer all questions on pigment use, but do provide additional insights.
2018
- EVALUATION OF QUANTITATIVE ELEMENTAL COMPOSITIONS AND ANTIOXIDANT POTENTIALS OF SPONDIAS MOMBIN EXTRACTS (LINN), A PRECURSOR AGAINST INFECTIOUS DISEASES
[Articolo su rivista]
Oludare Temitope, Osuntokun; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract
The purpose of this research work is to investigate the elemental composition and antioxidant potentials of Spondias mombin (leaf, root and stem bark) at concentration of 10, 20 and 5mg/ml. using different conventional laboratory methods, also to determine the antioxidant potentials of Spondias mombin. The element present are Sodium (Na), Calcium (Ca), Magnesium (Mg), Zinc (Zn), Iron (Fe), Lead (Pb), Copper(Cu), Manganese (Mn), Potasium (K) and Phosphorus (P).it was observed that all elements were present at appreciable quantity. It was observed that the highest and lowest quantity were found in Zinc (20.34) and Cu (1.22) for the leaf extract, Potasium (24.98) and (2.14) for stem bark, Calcium (29.35) and Pb (2.91) for the root extract. Pb has minimal quantity in all parts of Spondias mombin extract. P value< 0.0001, Significantly different standard deviations. The
antioxidant composition are FRAP, DPPH, Fe2+,ABTS, H2O2 and superoxide. The percentage composition of FRAP, DPPH, Fe2+,ABTS, SO and H2O2, superoxide phenol and flavonoid were elucidated, it was observed that ABTS has the highest composition in the stem bark and superoxide (SO) has the lowest content in the aqueous root extract of Spondias mombin.it can be deduced that Spondias mombin is a very important medicinal plant which should not go into extinction, its uses, efficacy and importance should not be over emphasis for the fact that it is rich in both elemental and antioxidants potential, therefore, its cultivation and day to day usage of Spondias mombin should be therefore be encouraged.
2018
- Indagine sui recipienti con pigmenti da domus pompeiane
[Relazione in Atti di Convegno]
Baraldi, P.; Baraldi, C.; Trojsi, G.
abstract
Negli ultimi 250 anni di scavi eseguiti nei siti di Pompei ed Ercolano sono stati rinvenuti numerosi pigmenti che sono serviti a dipingere e adornare le numerose ville alle falde del Vesuvio. Tali colori sono arrivati a noi, spesso, accuratamente conservati in ciotole, vasi, balsamari e altri piccoli contenitori fittili, in vetro e bronzo trovati all'interno di botteghe e abitazioni. Secondo il"Giornale degli Scavi di Pompei" della Soprintendenza Archeologica di Pompei, il primo scavo nella Regio l, lnsula 9 (l 9, 9) ebbe luogo nel 1952. Vicino agli scheletri di quattro individui, vennero trovate circa 150 ciotole globulari, fritilla e olle. La presenza di materiale all'interno costituisce un'opportunità per la ricostruzione della storia e delle tecniche pittoriche di Pompei e del mondo romano.
Sui contenuti sono stati applicati metodi molecolari di analisi, quali spettroscopia FT-lR e microscopia Raman, per l'identificazione della composizione. I risultati ottenuti consentono alcune considerazioni. Molti componenti quali quarzo, calcite, feldspati, diopside e pirite sono riferibili all'intonaco o ai prodotti dell'eruzione. L'aragonite presente massivamente puo' derivare da minerali bianchi, ma più probabilmente può essere dovuta alla macinazione di valve di molluschi. Ciò è importante per la comprensione dei decori bianchi su fondo colorato dei dipinti murali romani. ll pigmento blu è sempre a base di blu egiziano, mentre il verde può essere ottenuto mescolando un giallo e un blu; più frequentemente il verde è accertato come miscela di terra verde e blu egiziano. Malachite e azzurrile si ritrovano come prodotti di degrado di leghe metalliche a base di rame. Altri rari casi sono la cuprite, derivante da alterazione del rame e il litargirio, dall'alterazione di cerussite o piombo. La cerussite, identificata in alcuni contenitori, non è un pigmento per pitture murali: è noto da Plinio e da altri autori il suo uso come fondotinta, e questo può essere una prova della preparazione in I 9, 9 anche di contenitori per cosmetici.
2018
- Investigation of the pigment use in the Tomba dei Rilievi and other tombs in the Etruscan Banditaccia Necropolis. PIGMENTGEBRAUCH IM GRAB DER RELIEFS UND ANDEREN GRÄBERN DER ETRUSKISCHEN BANDITACCIA NEKROPOLE
[Abstract in Atti di Convegno]
Alfeld, M.; Baraldi, C.; Gamberini, M. C.; Walter, P.
abstract
The use of pigments in antiquity, by Romans, Greeks and Egyptians, has been subject to a number of scientific studies. That of contemporary cultures, such as the Etruscans, have been described only in a small number of publications. We investigated the pigment use in five tombs of the Banditaccia Necropolis, near Cerveteri in central Italy: Tomba dei Rilievi (4th century BC), Tomba Mengarelli (7th century BC), Tumolo Policromo (4th century BC), Tomba delle Onde Marine (4th-3rd century BC) and an yet untitled recently excavated tomb (4th century BC (preliminary)). All were carved from the soft tuff bedrock.
A special focus was put on the Tomba dei Rilievi (Tomb of the Reliefs. It is for up to 45 bodies with 13 loculus (burial niches) the largest of the investigated tombs and the only one decorated with painted stucco reliefs.
2018
- Le pitture parietali delle ville di Stabia: materiali e degrado
[Poster]
Baraldi, P.; Zannini, P.; Baraldi, C.; Tassi, L.; Rossi, A.; Troisi, G.
abstract
A partire dal 2009 con una serie di missioni in area stabiana, dopo il rilascio dei permessi da parte della Soprintendenza archeologica di Napoli e Pompei, sono state attuate indagini sulle pitture murali delle ville imperiali (Villa Arianna e Villa San lvlarco) per avere una descrizione dettagliata delle tecniche e dei materiali impiegati nelle pitture murali dei vari ambienti. Sono stati anche programmati controlli sul degrado dei materialj pittorici. Di concerto con archeologi e restauratori presenti sul sito, consapevoli delle operazioni di restauro attuate nel passato e tenendo conto dell'effetto degli eventi drammatici del 79 d.C., si è cercato di capire la situazione conservativa delle pitture per fornire indicazioni sulle operazioni di restauro. Nel corso delle missioni si sono osservate mediante microscopio digitale le superfici pittoriche divari ambienti e si sono effettuati dei microprelievi in posizioni marginali e rappresentative delle cromie presenti. Successivamente i campioni sono stati sottoposti ad analisi presso i laboratori universitari, ad analisi con varie tecniche analitiche e spettroscopìche di tipo atomico e molecolare, come la fluorescenza di raggi X (XRF). la spettroscopia FT-lR in trasmissione e in riflessione, la microscopia Raman con laser rosso e verde.
Una considerevole massa di dati ottenuta con i vari tipi di analisi permette di tracciare una sinossi delle tavolozze pittoriche degli artisti al lavoro, dello stato di conservazione dello strato pittorico, del degrado di alcuni dei pigmenti utilizzati in antico, e della presenza di materiali impiegati per il restauro nel corso dei decenni. Sono state evidenziate opere di mani differenti, in base all'impiego di tonalità realizzate con miscele di pigmenti e con sovrapposizione di materiali diversì. ln alcune aree il cinabro risulta virato in nero con produzione di solfocloruri di mercurio. Le decorazioni a mezzo fresco risultano spesso alterate e soggette a caduta di parti dello strato pittorico.
2017
- Application of micro-Raman spectroscopy for conservation projects in art and archaeology with a case study on Cappadocia rock-hewn wall paintings
[Articolo su rivista]
Baraldi, P.; Baraldi, C.; Pelosi, C.
abstract
This paper aims at reporting an overview of the principles and applications of micro-Raman spectroscopy in cultural heritage. Micro-Raman was used for characterizing painting pigments, inorganic binders, degradation materials in artworks with different goals: to know the materials and so the execution technique, to investigate the state of preservation, to establish the authenticity of the artefacts. The micro-Raman analyses were often performed on the occasion of conservative projects and they were able to supply valid and useful information to the conservators during their work. As case study, the project on the investigation of rock-hewn wall paintings in Cappadocia (Turkey) will be shortly presented as exemplificative of application of Raman techniques for the knowledge of the constituent materials, for supporting the conservation work and for detecting degradation products. Analysis were performed in the Interdepartmental instrument Center of Modena and Reggio Emilia University by a bench top system equipped with a microscope allowing for studying in non-destructive way different kinds of samples: powders, cross and thin sections, pre-treated samples.
2017
- Cyclodextrin-based nanosponges for the targeted delivery of the anti-restenotic agent DB103: A novel opportunity for the local therapy of vessels wall subjected to percutaneous intervention
[Articolo su rivista]
Coviello, Vito; Sartini, Stefania; Quattrini, Luca; Baraldi, Cecilia; Gamberini, Maria Cristina; La Motta, Concettina
abstract
Nano-sized colloidal carriers represent innovative drug delivery systems, as they allow a targeted and prolonged release of poorly water-soluble drugs, improving their bioavailability and modifying their pharmacokinetic parameters. In this work we describe cyclodextrin-based nanosponges, obtained through polimerization of β-cyclodextrin with diphenyl carbonate as the cross-linking agent, loaded with a novel multi-effective heterocyclic compound, DB103, able to regulate key cellular events involved in the remodelling of vessels wall. Fabrication and drug-loading procedures, as well as physical-chemical characterization and drug-release profile of the novel colloidal system are reported. Results achieved demonstrate the ability of nanosponges to enclose efficiently the target drug and release it slowly and continuously, thus suggesting the exploitability of the novel system for the local therapy of vessels wall subjected to percutaneous intervention.
2015
- A Raman investigation of ancient Colliria
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Pietro; Deviese, Tibaut; Baraldi, Cecilia; Tinti, Anna
abstract
In January 1884, in Atestino territory (PD-Este, northern of Italy), was discovered in Morlungo district, where is present the southern necropolis aged in pre-Roman and Roman period (Ateste), a tomb dated to the second half of the I sec d.C (Tomb civic IX) whose furnishings exhibition being a doctor-surgeon-apothecary (Simonetta Bonomi - "Medici in Este romana. 3. La tomba del medico” Aquileia nostra”, 55, 1984, p. 78-108.). Among the various finds is present a bronze box (capsula), several medicinal preparations in the solid state form were also found inside. They were collyria (from the greek = κολλύριον small pills solid elongated), not necessarily used in ophthalmologic practice (Celse V 28 G; Hippocrates, Mul. I 51).
In bibliography, rare are the articles published regarding the discovery of these findings, but even more rare are articles on collyria chemical analysis.
In this study, 17 collyria / fragments of collyria exposed in Este National Museum and other six fragments from the tomb of a physician and stored in warehouses, using non-invasive and non-destructive techniques were analyzed in-situ. Raman microscopy, FT-IR spectroscopy and X-ray Fluorescence techniques were chosen for the analysis using portable equipments.
In this study we report the preliminary composition data of these remains. The analyzes performed, chemical charaterized several components already identified to the specific literature on these findings: calcite, indrocerussite, litharge, cuprite, tenorite, azzurite, realgar, pararealgar, orpiment. Moreover in this work some components, not analyzed in collyria forms yet, were also identified: pyrite and alumina.
In the next future could be interesting study the remains with micro-invasive techniques, this in order to better investigate the organic component present and complete the knowledge of these rare and interesting archaeological finds, on which many questions still remain open and unanswered.
2015
- An approach to the identification of ambers from different archaeological sites (P1)
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Pietro; Deviese, Thibaut; Baraldi, Cecilia; Tinti, Anna; Pacciarelli, Marco
abstract
Chemical studies on resinous materials in archaeological remains are generally aimed at identifying the origin of the materials present, at studying the production and manufacturing techniques, and at improving techniques for their conservation and restoration.
This is particularly true for ambers remains. This paper presents some significant results for a systematic characterisation of the chemical composition of ambers of different provenance. The study has been carried out by using spectroscopic techniques, Raman and FT-IR with the aim of creating or extend FT-IR, Raman, FT-Raman libraries of geological and archaeological ambers. The data could be used as references in provenance studies of archaeological amber finds.
Based on this knowledge, archaeological resinous materials, recovered in a various sites, dating back from the ninth century BC to the second century AD, have been analysed and the relevant results discussed. Comparisons of analytical detailed results enable the recent and ancient history of the materials to be traced.
It is shown that provenance can be ascertained, in addition to the classical Beck’s method of FT-IR spectra (based on the special shape of the infrared spectrum in the 1500- 1000 cm-1 region), also by using Raman spectra and XRF data. The alteration of Museum preserved samples are taken into consideration for a description of the rapid changes of the spectra recorded.
2015
- An approach to the identification of ambers from different archaeological sites (Part 2)
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Pietro; Deviese, Thibaut; Baraldi, Cecilia; Tinti, Anna; Pacciarelli, Marco
abstract
Chemical studies on resinous materials in archaeological remains are generally aimed at identifying the origin of the materials present, at studying the production and manufacturing techniques, and at improving techniques for their conservation and restoration.
This is particularly true for ambers remains. This paper presents some significant results for a systematic characterisation of the chemical composition of ambers of different provenance. The study has been carried out by using spectroscopic techniques, Raman and FT-IR with the aim ofcreating or extend FT-IR, Raman, FT-Raman libraries of geological and archaeological ambers. The data could be used as references in provenance studies of archaeological amber finds.
Based on this knowledge, archaeological resinous materials, recoveredin a various sites, dating back from the VI century BC to the second centuryAD, have been analysed and the relevant results discussed. Comparisons of analytical detailed results enable the recent and ancient history of the materials to be traced.
It is shown that provenance can be ascertained, in addition to the classical Beck’s method of FT-IR spectra (based on the special shape of the infrared spectrum in the 1500- 1000 cm-1 region), also by using Raman spectra and XRF data. The alteration of Museum preserved samples are taken into consideration for a description of the rapid changes of the spectra recorded.
2015
- Experimental and theoretical SERS spectra: the case of Ampicillin
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Cecilia; Tinti, Anna; Ottani, Stefano
abstract
Surface enhanced Raman scattering (SERS) spectroscopy is a powerful tool for the study of structure, symmetry and orientation of molecules adsorbed on metal surfaces. It is a highly sensitive technique useful to detect species present at a trace level concentrations and to gather information concerning metal-adsorbate interactions. The study of drug molecules adsorbed on metallic substrate is becoming critical in future applications like drug delivery, bio-active surfaces, bio and chemical nano-sensors, etc. Moreover, the study of interaction of drug molecules with metals in solution can provide useful information on the biological activity of such molecules.
Ampicillin or 6-[D(-)α-aminophenylacetamido] penicillanic acid is a well-known penicillin class antibiotic with betalactamic structure, which is getting new attention for drug resistance problems. In the past we have studied the existing polymorphic and solvate forms by different analytical techniques and by comparing experimental and theoretical data (C. Baraldi, A. Tinti, S. Ottani, M.C. Gamberini, J. Pharm. Biomed. Analysis 100 (2014) 329-340).
In this work, ampicillin SERS spectrum at 10-4 M concentration was studied and discussed. The adsorption geometry of the ampicillin molecule on colloidal silver surface was deduced from the SERS selection rules. In addition, Density Functional Theory (DFT) computations on a couple of Ag atoms or AgCl interacting with different ampicillin groups were performed, to obtain theoretical spectra for the interpretation of the SERS experiments. Interactions with Ag colloidal surfaces have been approximated by placing an Ag2 cluster in positions close to electron donor groups of the ampicillin molecule (i.e. the carboxylic group (zwitterion), the sulfur atom (zwitterion), the aromatic ring (zwitterion), the -NH2 group (anion) and the tautomeric -COOH/-NH2 group). For the ampicillin the aug-cc-pVDZ (aug-cc-pV(D+d)Z for Sulfur atom) basis set was used, whereas the Ag atoms were modeled by the lanl2dz basis set. Calculations were performed with an implicit solvent model (CPCM). Computations led to stable optimized geometries with the exception of -NH3+/Ag2 (viz. the ampicillin in zwitterionic form) since such a group has a marked electrophilic character. Interpretation of the theoretical frequency spectra was performed by the Potential Energy Distribution (PED) analysis of the fundamental vibrations modes.
According to the theoretical results, SERS experiments demonstrated that ampicillin was adsorbed in tilted orientation on silver colloid; the interaction mainly takes place by means of the benzenic ring and the aminic group.
2015
- Pigments and cosmetics from Regio I, Insula 9 (I,9,9): archaeometrical analyses
[Relazione in Atti di Convegno]
Baraldi, Pietro; Baraldi, Cecilia; Trojsi, Giorgio
abstract
After a review of the color containers found in Pompeii, a group of them coming from the Officina Pigmentaria is considered. A large amount of data concerning the contents of bowls of different kinds found in a Pompeiian house is presented. Many materials are encountered that can be classified in many ways. Some distinctions could be based on the nature of the possible contents at the time of the Vesuvius eruption in 79 A. D. A statistical evaluation of the frequencies of attestation of different materials suggests some hypotheses. A possible interpretation of the house as being a shop for preparing pigments, cosmetics and drugs is advanced.
2015
- The ampicillin experimental and theoretical SERS spectra
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Cecilia; Tinti, Anna; Ottani, Stefano
abstract
Surface enhanced Raman scattering (SERS) spectroscopy is a powerful tool for the study of structure, symmetry and orientation of molecules adsorbed on metal surfaces. It is a highly
sensitive technique useful to detect species present at a trace level concentrations and to gather information concerning metal–adsorbate interactions. The study of drug molecules adsorbed on
metallic substrate is becoming critical in future applications like drug delivery, bio-active surfaces, bio and chemical nano-sensors, etc. Moreover, the study of interaction of drug molecules with metals in solution can provide useful information on the biological activity of such molecules. Ampicillin or 6-[D(-)α-aminophenylacetamido] penicillanic acid is a wellknown penicillin class antibiotic with betalactamic structure, which is getting new attention for drug resistance problems. In the past we have studied the existing polymorphic and solvate forms by different analytical techniques and by comparing experimental and theoretical data [1].
In this work, ampicillin SERS spectrum at 10-4 M concentration was studied and discussed. The adsorption geometry of the ampicillin molecule on colloidal silver surface was deduced from the SERS selection rules. In addition, Density Functional Theory (DFT) computations on a couple of Ag atoms or AgCl interacting with different ampicillin groups were performed, to obtain theoretical spectra for the interpretation of the SERS experiments. Interactions with Ag colloidal surfaces have been approximated by placing an Ag2 cluster in positions close to electron donor groups of the ampicillin molecule (i.e. the carboxylic group (zwitterion), the sulfur atom (zwitterion), the aromatic ring (zwitterion), the –NH2 group (anion) and the tautomeric –COOH/–NH2 group). For the ampicillin the aug-cc-pVDZ (aug-cc-pV(D+d)Z for Sulfur atom) basis set was used, whereas the Ag atoms were modeled by the lanl2dz basis set. Calculations were performed with an implicit solvent model (CPCM). Computations led to stable optimized geometries with the exception of –NH3+/Ag2 (viz. the ampicillin in zwitterionic form) since such a group has a marked electrophilic character. Interpretation of the theoretical frequency spectra was performed by the Potential Energy Distribution (PED) analysis of the fundamental vibrations modes. According to the theoretical results, SERS experiments demonstrated that ampicillin was adsorbed in tilted orientation on silver colloid; the interaction mainly takes place by means of the benzenic ring and the aminic group.
2014
- A study of some illuminated Armenian manuscripts
[Abstract in Atti di Convegno]
Keheyan, Yeghis; Baraldi, Pietro; Zannini, Paolo; Eliazan, Gayane; Baraldi, Cecilia; Gamberini, Maria Cristina; Nunziante, Stella
abstract
Due to its early Christianization, Armenia has preserved a huge patrimony of religious figures in paintings, statues, icons and illuminated codices. Most of the latter are still conserved in Matenadaran Library in Yerevan and their chronology is widely represented from the Middle Ages to XIX century. Armenian manuscripts embrace also various humanities, such as history, philosophy, law, medicine and mathematics. A rich historiographic literature is also present. Therefore it was attractive to carry out an attempt to discover materials and techniques used in the past to prepare the manuscripts and to assemble the codices. Inks and gilding were also considered. Specific materials of Armenian culture will be emphasized. The samples were taken by some of us at the Matenadaran Library of Yerevan (Armenia) and some additional materials, such as Armenian bole and cochineal powder, were found in Yerevan too. The samples were taken with a lancet on deteriorated portions of some papers and parchments pertaining to Armenian codices. Only small fragments were used, since the spectroscopic techniques used need amount down to some micrograms. This is due to their high spatial resolution, enabling also the overlapping layers of pigments and preparation to be studied and their molecular identity to be ascertained in a non-destructive non –invasive way: the same samples could be subjected to other analyses with other techniques. The use of so small samples enabled the use of high performance instrumentation in the Centre of Great Instruments in Modena (CIGS) and to carry out additional experiments with silver nano-particles for Sers technique (surface enhanced Raman spectroscopy). Fourier-Transform infrared (FTIR) spectra were recorded using an Alpha FT-IR spectrometer (Bruker) equipped with the Diffuse Reflection Infrared Fourier Transform ( DRIFT) module in the spectral range 7500 – 375 cm-1 at a resolution of 2 cm-1 cumulating at least 200 scans. The use of SEM-EDX technique was important for characterization of papers and inks. Py/GS/MS was fundamental for organic binding media characterization. The methods of study were the application of atomic (XRF X-ray fluorescence spectroscopy), molecular (FT-IR and microRaman), SEM-EDX and pyrolisis GS/MS spectroscopic techniques to the samples in such a way to obtain the information useful for the understanding of the materials and art techniques applied. Particularly, the analysis of the different inks used in different times and the decoration with gilding on bole with a proper binder was taken into consideration.
Experimental Results. Many materials were seen to be used through centuries in Armenian illumination. As already pointed out by Orna and co-workers [1, 2] many materials were identified and the execution techniques were clarified. According to recent investigation [3] other results on new materials and specific products coming from the territory have appeared based on Raman microscopy. A rich polychromy was often present and rare materials are shown to have been employed, such as the green antlerite, a basic copper sulfate mineral present in Caucasus and South of Iran. Lazurite, vermilion, azurite, orpiment, white lead, red lead, indigo, litharge, massicot, carbon were identified. Gilding was applied on an assisa. The Armenian bole is shown to be composed of white Kaolinite and Hematite.
Forthcoming information is the application of Raman Sers technique for the identification of the materials and techniques used in Armenian illumination through times. The Armenian Cochineal (from Porphyrophora hamelii Brandt) is composed of carminic acid, that is highly fluorescent in Raman microscopy, unless Sers is used on a sample. With the application of simple atomic and molecular spectroscopy techniques available in many laboratories it was shown to be possible to obtain fundamental information on the specificity of Armenian illuminati
2014
- ARMENIAN ILLUMINATED MANUSCRIPTS, A COLOURFUL TESTIMONY OF RELIGIOUS ART EXAMINED BY MOLECULAR SPECTROSCOPY TECHNIQUES
[Relazione in Atti di Convegno]
Baraldi, Pietro; Yeghis, Keheyan; Gayane, Eliazan; Andranik, Mkrtichian; Stella, Nunziante; Baraldi, Cecilia
abstract
Proceeding in the analysis of the painting materials and techniques of Armenian illuminated manuscripts we refer about a XIV century manuscript with colourful images that were under restoration. Some
microsamples were analyzed with microRaman spectroscopy and showed that traditional pigments were used, but some products and mixtures are typical of Armenia illumination, such as vergaut a mixture of indigo and orpiment.
2014
- Characterization of polymorphic ampicillin forms
[Articolo su rivista]
Baraldi, Cecilia; Tinti, A; Ottani, S; Gamberini, Maria Cristina
abstract
In this work polymorphs of α-aminobenzylpenicillin (ampicillin), a β-lactamic antibiotic, were prepared and investigated by several experimental and theoretical methods. Amorphous monohydrate and three crystalline forms, the trihydrate, the crystal form I and the crystal form II, were investigated by FT-IR and micro-Raman. Also data obtained by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray powder diffraction (XRPD) and hot-stage Raman spectroscopy are reported. Finally, quantum mechanical calculations were performed by density functional theory (DFT) to assist the assignment of spectroscopic experimental bands. For the first time, the ampicillin molecule in its zwitterionic form was studied at the B3LYP/aug-cc-pVDZ level and the corresponding theoretical vibrational spectra were computed. In fact, ampicillin in the crystal is in zwitterionic form and concentrations of this same form are quite relevant in solutions at physiological pH. Experimental and theoretical results allowed identification of specific features for polymorph characterization. Bands typical of the different polymorphs are identified both in IR and Raman spectra: in particular in the NH stretching region (IR), in the amide I+δNH region (both techniques), in the 1520-1490cm(-1) region (IR), in the 1320-1300cm(-1) and 1280-1220cm(-1) (IR), in the 1200-1170cm(-1) (Raman), in the amide V region (IR), and, finally, in the 715-640cm(-1) and 220-200cm(-1) (Raman). Interconversion among different polymorphs was investigated by hot-stage Raman spectroscopy and thermal analysis, clarifying the complex pattern of transformations undergone as a function of temperature and heating rate. In particular, DSC scans show how the trihydrate crystals transform into anhydrous forms on heating. Finally, stability tests demonstrated, after a two years period, that no transformation or degradation of the polymorphs occurred.
2014
- Study of Black Core, ceramic tile’s defect, by a multi technique approach
[Relazione in Atti di Convegno]
Ferrari, Giorgia; Zannini, Paolo; Baraldi, Cecilia
abstract
The traditional ceramic industrial production, for most of its applications, i.e. Ceramic Tiles, Heavy Clay Products, Tableware and Sanitaryware, is often affected by the formation, during the firing process, of a dark color core, normally named “Black Core”, that can represent an aesthetical and technological problem.
The true nature of this defect was never clearly stated, but it is known to be due to the presence of chromophores, like Iron, and organic or reducing materials, combined with a lack of permeability of the unfired body.
A novel, mullti-approach study was made by XRD, XRF, SEM-EDS, FTIR and Mossbauer Spectroscopy, and by micro Raman spectroscopy and mapping, with the aim to clarify the morphology, the composition and the Iron oxidation state of this inner layer.
Possible solutions were suggested, by the addition to the recipe of proper additives.
2013
- Experimental and theoretical study of polymorphic and solvate ampicillin forms
[Abstract in Atti di Convegno]
Baraldi, Cecilia; L., Galavotti; A., Tinti; S., Ottani; Gamberini, Maria Cristina
abstract
In literature, many active pharmaceutical ingredients (APIs) are known to crystallize in different crystalline packings (polymorphs) or with solvent molecules as an integral part of their structures (pseudopolymorphs). In a pharmaceutical dosage form, the active ingredient solid-state phase identity or conversion could dramatically alter the final pharmaceutical properties. In particular, the solid state administrated drug can influence important properties like bioavailability. In this study four α-aminobenzylpenicillin [1-3] forms were crystallized [4,5] and the molecular vibrations of the various ampicillin forms were investigated by ATR/FT-IR [2,3], micro-Raman and SERS (surface enhanced Raman spectroscopy) [4] spectroscopies (firstly reported). The HSRM (hot stage Raman microscopy) was also able to follow the transition from the trihydrate ampicillin to the amorphous monohydrate. DSC, TGA, XRPD data were also afforded [1,4,5]. For the first time, the Raman spectra of the four ampicillin forms are reported. Finally, for assisting experimental assignment bands quantum mechanical calculations were also performed and the density functional theory (DFT) predictions were used [6,7].
References:
[1] E. Shefter et al., J. Pharm. Sci. 62/5 (1973) 791.
[2] M. N. J. James et al. Nature 220 (1968), 168.
[3] E. Ivashkiv, In: Analytical Profiles of Drug Substances, vol. 2., (1973) Academic Press, New York, K. Florey, (Ed.).
[4] K. W. B. Austin et al., Nature 208 (1965) 999.
[5] Parker et al., 1976, USP 3933796.
[6] A. D. Becke, J. Chem. Phys. 98 (1993) 5648–5652.
[7] W. T. Yang, R. G. Parr, Phys. Rev. B 37 (1988) 785–789.
2013
- Experimental and theoretical study of polymorphic and solvate ampicillin forms
[Abstract in Atti di Convegno]
Baraldi, Cecilia; L., Galavotti; A., Tinti; S., Ottani; Gamberini, Maria Cristina
abstract
In literature, many active pharmaceutical ingredients (APIs) are known to crystallize in different
crystalline packings (polymorphs) or with solvent molecules as an integral part of their structures
(pseudopolymorphs). In a pharmaceutical dosage form, the active ingredient solid-state phase identity or
conversion could dramatically alter the final pharmaceutical properties. In particular, the solid state
administrated drug can influence important properties like bioavailability. In this study four α-
aminobenzylpenicillin forms were crystallized and the molecular vibrations of the various ampicillin forms
were investigated by ATR/FT-IR, micro-Raman and SERS (surface enhanced Raman spectroscopy)
spectroscopies (firstly reported). The HSRM (hot stage Raman microscopy) was also able to follow the
transition from the trihydrate ampicillin to the amorphous monohydrate. The same technique allowed of
controlling the solid-solid convertion from trihydrate to anhydrous forms. DSC, TGA, XRPD data were also
afforded. For the first time, the Raman spectra of the four ampicillin forms are reported. Finally, for assisting
experimental assignment bands quantum mechanical calculations were also performed and the density
functional theory (DFT) predictions were used.
2013
- IR, Raman and SERS spectra of propantheline bromide
[Articolo su rivista]
Baraldi, Cecilia; Freguglia, Giada; A., Tinti; M., Sparta; A. N., Alexandrova; Gamberini, Maria Cristina
abstract
The two known propantheline bromide polymorphs (form I and form II) were studied and characterized
by a multianalytical approach. In the present work, the identification of propantheline bromide polymorphic
forms through vibrational IR spectroscopies are presented and for the first time Raman microscopy
and hot stage Raman microscopy (HSRM) studies are reported. Finally, quantum mechanical calculations
were performed. For assisting the assignment of the experimental picks, the two IR spectra of the most
and least stable representatives of a set of 56 conformers are calculated and studied.
DSC thermograms data, are also reported. The surface enhanced Raman scattering (SERS) spectrum was
also recorded in a silver colloid; it could be inferred that propantheline bromide is adsorbed on silver colloid
through the oxygen atom with the molecular plane perpendicular to the metal surface.
2013
- Phoenicians preferred red pigments: micro-Raman investigation on some cosmetics found in Sicily archaeological sites
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Giada, Freguglia; Elsa Van, Elslande; Pamela, Toti; Baraldi, Pietro; Gamberini, Maria Cristina; Claudia, Pelosi
abstract
This research was undertaken in the aim of identifying and getting deeper knoowledge into materials and pigments used in cosmestics concerning the contest of the phoenician settlements in Sicilian territory. In fact, about the typologies of cosmetics in use among the Phoenicians, little is known. On this subject, generally references come from bibliographic latin sources: in antiquity, women preferred to paint white their face, red lips and cheeks, yellowish eyes and black to sorround their look (Pliny the Elder, Naturalis Historia; Ovidius, De medicamine faciei feminae). An interesting aspect of this research is that just one paper is known on Punic cosmetics.[1]
In the Museo Archeologico Regionale “Antonino Salinas” (Palermo, Sicily) an important collection of unguentaries coming from the town of Selinunte is preserved. Some of them, finely crafted, come from the sanctuary of Demetra Malophoros, some unguentaries come from the acropolis and some more from the necropolis (dating from the 6th to the 5th century b. C). The sacred area, excavated by Cavallari (1818) and Salinas (1903-1905), have provided a great amount of archaeological materials. In the area where once the acropolis rose, the remains show a mixed village, Phoenician and Greek. In this study, the findings from Salinas were considered, as well as some others from the Museum Conte Agostino Pepoli (Trapani), from the Museum Baglio Anselmi (Marsala) and from the museum of Mozia. The number of glass and fictile unguentaries, pyxis and alabastra examined were large: 142 items from Salinas, 210 from Mozia, 14 from Pepoli and 117 from Baglio Anselmi.
This research has completed the one carried out on 210 samples from the Museum of Whitaker Foundation from Mozia, a merely phoenician –punic settlement.[2,3]
The samples were analyzed by spectroscopic techniques.
The IR spectra were acquired with a spectrophotometer VERTEX 70 (Bruker) FT-IR, equipped with a detector deuterium triglycine sulphate (DTGS). The setting parameters were: resolution 4 cm-1, spectral range 4000-600 cm-1, number of scans 32. ATR spectra were recorded using an Elmer Golden-Gate accessory.
The micro-Raman spectrometer used in this case was a Labram Model from the Jobin Yvon-Horiba with a spatial resolution of 1 µm and with quick detection ability as a result of the CCD detector 1024x256 pixels cooled to -70°C by the Peltier effect. The spectral resolution was 1 cm-1. The exciting wavelength was the 632.8 nm red line of a He-Ne laser.
Generally the samples were presented as inorganic powders of different colors: white, black, blue and red. Though the samples came from different museums, they were considered togheter, since they belonged all to the Phoenician culture and coming from Trapani archaeological sites.
The white samples were of two types. The first one was mainly composed of gypsum and anhydrite mixtures (e.g. Inv No 1680, 1663, 1753); the other type (e.g. pyxes Inv N° 1393, 1451) was composed of fully carbonated cerussite, gypsum and litharge. The second kind of cosmetic corresponded to the most famous Greek cosmetic, called psymition, used by women to white the skin. The first type suggested that, for the same use, alternative materials, cheaper and most readily available, could be employed in the past.
The black powders, usually used to outline the eyes, were mostly given by carbon obtained from vegetable combustion (e.g. Inv. N° 1566, 2314, 4313) or, sometimes, from bone combustion (animal charcoal) as for the samples Inv. N° 3140, 1761.
A single blue powder (Inv N° 42259) was consisted by the famous Egyptian blue (CaCuSi4O10).
The love for the red color by Phoenician is evident from the great number of powders of this color, probably used to give color to the cheeks or lips. A wide variety of red minerals was found. In many cases the presence of hematite (e.g. Inv N° 2309, 2689, 4269) was detected.
A large number of pink and r
2013
- Structural, electronic, thermodynamical and charge transfer properties of Chloramphenicol Palmitate using vibrational spectroscopy and DFT calculations
[Articolo su rivista]
Rashmi, Mishra; Anubha, Srivastava; Anamika, Sharma; Poonam, Tandon; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract
The global problem of advancing bacterial resistance to newer drugs has led to renewed interest in the use of Chloramphenicol Palmitate (C27H42Cl2N2O6) [Palmitic acid alpha ester with D-threo-(-),2-dichloro-N-(beta-hydroxy-alpha-(hydroxymethyl)-p-nitrophenethyl)acetamide also known as Detereopal].
The characterization of the three polymorphic forms of Chloramphenicol Palmitate (CPP) was done spectroscopically by employing FT-IR and FT-Raman techniques. The equilibrium geometry, various bonding features, and harmonic wavenumbers have been investigated for most stable form A with the help of DFT calculations and a good correlation was found between experimental data and theoretical values. Electronic properties have been analyzed employing TD-DFT for both gaseous and solvent phase.
The theoretical calculation of thermodynamical properties along with NBO analysis has also been performed to have a deep insight into the molecule for further applications.
2012
- Ampicillina: studio vibrazionale mediante FT-IR, micro-Raman e SERS di forme solvate e polimorfe
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; A., Tinti; Baraldi, Pietro
abstract
Dalla letteratura è noto che numerosi principi attivi farmaceutici (APIs) tendono a cristallizzare in differenti impaccamenti cristallini (polimorfi) oppure comprendendo molecole di solvente come parte della struttura cristallina (pseudopolimorfi). All’interno di una formulazione farmaceutica, l’identità o la possibilità di conversione del’API potrebbe alterare le caratteristiche e l’efficacia della forma farmaceutica, in particolare portando a differente biodisponibilità.L’ampicillina o α-aminobenzylpenicillina o 6-[D (-)-α aminophenylacetamido] penicillanic acid esiste come forma anidra (attestate 2 forme polimorfe) ed in altre forme idrate, in particolare triidrata e monoidrata. All’interno delle diverse formulazioni farmaceutiche in commercio, come polveri per uso iniettabile o orale, oppure come compresse o capsule, l’ampicillina è presente come forma triidrata, talora come anidra o come sale sodico.Dalla letteratura è noto che numerosi principi attivi farmaceutici (APIs) tendono a cristallizzare in differenti impaccamenti cristallini (polimorfi) oppure comprendendo molecole di solvente come parte della struttura cristallina (pseudopolimorfi). All’interno di una formulazione farmaceutica, l’identità o la possibilità di conversione del’API potrebbe alterare le caratteristiche e l’efficacia della forma farmaceutica, in particolare portando a differente biodisponibilità.L’ampicillina o α-aminobenzylpenicillina o 6-[D (-)-α aminophenylacetamido] penicillanic acid esiste come forma anidra (attestate 2 forme polimorfe) ed in altre forme idrate, in particolare triidrata e monoidrata [1-3]. All’interno delle diverse formulazioni farmaceutiche in commercio, come polveri per uso iniettabile o orale, oppure come compresse o capsule, l’ampicillina è presente come forma triidrata, talora come anidra o come sale sodico.Il presente studio ha compreso la cristallizzazione e la caratterizzazione delle varie forme polimorfe e solvate dell’ampicillina. La forma triidrata, la monoidrata (detta forma A) e la forma anidra γ (o forma B) sono state ottenute con tecniche riportate in letteratura [4]. Per la forma δ, meno nota e studiata (sono riportati XRPD e IR) si è seguito il metodo di cristallizzazione riportato da Parker et al. [5]. Tali metodi di cristallizzazione (forme A, B, δ) hanno portato ad un prodotto finale di colore giallo chiaro, che potrebbe indicare decomposizione dei campioni [1]. In questo lavoro viene riportato come le due forme anidre siano state cristallizzate da riscaldamento in un capillare sigillato: a seconda della velocità diriscaldamento si sono ottenute la forma y (riscaldamento lento) e δ (riscaldamento rapido) senza alcun cambiamento di colore della polvere (cristalli bianchi). Le forme ottenute allo stato solido sono poi state caratterizzate mediante differenti tecniche analitiche (FT-IR, XRPD e DSC) ed i dati sperimentali sono stati confrontati con la bibliografia [1,4,5]. Inoltre, le differenti forme sono state studiate anche mediante la microscopia Raman (laser 632 nm). Per la prima volta in questo studio viene riportato uno studio SERS della molecola di ampicillina, utilizzando una soluzione colloidale di nanoparticelle d’argento secondo Lee e Meisel [6]. L'uso della Hot Stage Raman Microscopy (HSRM) ha permesso di seguire il passaggio dalla forma triidrata ad ampicillina monoidrata amorfa. Inoltre, con la stessa tecnica si sono potute studiare le trasformazioni solido-solido dal triidrato alle due forme anidre.Bibliografia[1] E. Shefter et al., J. Pharm. Sci. 1973, 62/5 791.[2] M.N.J. James et al. Nature 1968, 220 168.[3] E. Ivashkiv, In: Analytical Profiles of Drug Substances, vol. 2., Academic Press, New York, K. Florey, (Ed.), 1973.[4] K.W.B. Austin et al., Nature 1965, 208, 999.[5] Parker et al., 1976, USP 3933796.[6] P.C. Lee and D. Meisel J. Phys. Chem. 1982, 86, 3391.
2012
- Analisi micro-Raman di polveri cosmetiche greche e puniche
[Abstract in Atti di Convegno]
Freguglia, Giada; Baraldi, Cecilia; Gamberini, Maria Cristina; E., Van Elslande; Baraldi, Pietro
abstract
Presso il Museo Archeologico Regionale “Antonino Salinas” di Palermo è conservato un importante nucleo di balsamari provenienti da Selinunte. Taluni, di pregevole manifattura, provengono dal Santuario di Demetra Malophoros. Altri unguentari e balsamari provengono dall’acropoli, altri ancora dalle necropoli. Appartengono ad un periodo compreso tra la metà del VI e la metà del V secolo a. C. L’area sacra, messa in luce durante gli scavi effettuati da Cavallari nel 1818 e da Salinas nel 1903-1905, ha portato alla luce una quantità immensa di materiali archeologici. Nell'area dove prima sorgeva l'acropoli i resti presentano un abitato misto, punico e greco. Al fine di questo studio sono stati inoltre presi in esame anche altri campioni, conservati nei saloni espositivi e in magazzino, provenienti dall’isola di Mozia, insediamento prettamente fenicio-punico.Gli insediamenti da cui provengono i contenitori, Selinunte e Mozia, offrono una gamma di valenze culturali assai variegata che sta a confermare il loro carattere di insediamenti nati da e per lo scambio. Le analisi condotte nel presente lavoro fanno seguito a quelle relative ad un importante gruppo di contenitori cosmetici di età Punica, coevi a quelli qui studiati, conservati presso il Museo della Fondazione Withaker sull’isola di Mozia [1,2].Il nucleo di balsamari fittili e vitrei, pissidi e alabastra considerati è stato ispezionato e si sono raccolte polveri di vari colori.La microscopia Raman ha permesso di identificare e caratterizzare i residui. Campioni bianchi hanno rivelato essere composti prevalentemente da miscele di gesso e anidrite (n inv. 1680, 1663, 1753). Le pissidi n. 1393 e 1451 presentavano residui bianchi composti da cerussite completamente carbonatata, gesso e litargirio. Si tratta del cosmetico greco per eccellenza, denominato psymition, utilizzato dalle donne per conferire pallore all’incarnato.Polveri rosa contenute in balsamari figurati di origine greca hanno mostrato come componenti ematite, quarzo, calcite, anatasio e goetite oppure, nel caso dell’askos zoomorfo n. 610, calcite, ossido di piombo, ematite, carbone e residuo organico. Il contenitore in vetro policromo n. 34228 presentava un abbondante residuo rosso composto da magnetite, quarzo, silicati ed ematite. Una conchiglia del genere Pecten (n. 34396) mostrava residui rossi composti da ematite, magnetite, lepidocrocite, goetite e tracce di cinabro (HgS). Un’interessante polvere rossa, (HgS miscelato con anatasio) è stata rinvenuta all’interno dell’ alabstron n. 7317/7 proveniente dalla necropoli di Marsala (tomba n.34). Risultati simili si sono ottenuti nell’ambito delle precedenti indagini su Mozia relative a contenitori della stessa tipologia. Il rinvenimento di questi pigmenti in associazione ad alasbatra è interessante in quanto la letteratura generalmente indica l’uso dedicato di questi particolari contenitori ad unguenti e profumi. Le analisi del contenuto azzurro della coppetta fittile n. 42259 hanno rilevato la presenza del celebre blu egiziano (CaCuSi4O10).Bibliografia[1] G. Freguglia, C. Baraldi, M.C. Gamberini, P. Toti, P. Baraldi,; PRIN07- Colors and balms in antiquity: from the chemical study to the knowledge of technologies in cosmetics, painting and medicine. Aboca, Sansepolcro (Arezzo, Italy), 2-3th December 2010, p. 50-51[2] C. Baraldi, G. Freguglia, M.C. Gamberini, P. Baraldi, RAA2011 Parma 5-8th September 2011, pp. 103-104;
2012
- Chemico-physical investigation of tenofovir loaded polymeric nanoparticles
[Articolo su rivista]
Belletti, Daniela; Tosi, Giovanni; Forni, Flavio; Gamberini, Maria Cristina; Baraldi, Cecilia; Vandelli, Maria Angela; Ruozi, Barbara
abstract
Tenofovir (PMPA), an acyclic nucleoside phosphonate analog, is one of the most important drugs used for
the HIV treatment. Unfortunately, several adverse reactions are related to its i.v. administration owing
to the saturation of an anionic renal transporter. In order to improve the drug administration, the PMPA
was embedded into a new type of nanocarriers based on poly-(d,l-lactide-co-glycolide) (PLGA) and/or
chitosan (CH). The strategies for the preparation of nanoparticles (Nps) with a more efficient drug loading
respect to the one reported in the literature for PMPA nanoencapsulation were investigated. CH was
added in the first inner emulsion or in the external phase during the second emulsion of water/oil/water
(W/O/W) Nps. The addition of CH in the first inner emulsion was the most promising technique. The
Nps have a Z-average of 230 nm, a Z-potential of
−3 mV and an EE% of 15 that was 2.5–3 times higher
than that obtained with PLGA Nps or CH Nps. In vitro release studies showed a limited control on drug
release in phosphate buffer (pH 7.4) while an initial burst effect followed by a slow drug release was
observed in acidic receiving phase (pH 4.6). These results suggest the PLGA/CH Nps should be an effective
and attractive anti-HIV drug carrier to study the cellular uptake and drug delivery on target cells such as
macrophages.
2012
- Intermolecular charge transfer and vibrational analysis of hydrogen bonding in acetazolamide.
[Articolo su rivista]
Deepika, Chaturvedi; Vineet, Gupta; Poonam, Tandon; Anamika, Sharma; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract
In the present work the structural and spectral characteristics of acetazolamide have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. Based on these results, we have discussed the correlation between the vibrational modes and the structure of the dimers of acetazolamide. The calculated vibrational spectra of three dimers of acetazolamide have been compared with observed spectra, and the assignment of observed bands was carried out using potential energy distribution. The observed spectra agree well with the values computed from the DFT. A comparison of observed and calculated vibrational spectra clearly shows the effect of hydrogen bonding. The frequency shifts observed for the different dimers are in accord with the hydrogen bonding in acetazolamide. Natural bond orbital (NBO) analyses reflect the charge transfer interaction in the individual hydrogen bond units and the stability of different dimers of acetazolamide.
2011
- A multi-analytical approach for the characterization of powders from the Pompeii archaeological site
[Articolo su rivista]
C., Canevali; P., Gentile; M., Orlandi; F., Modugno; J. J., Lucejko; M. P., Colombini; L., Brambilla; S., Goidanich; C., Riedo; O., Chiantore; Baraldi, Pietro; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract
Nine black powders found in Pompeii housesin three different types of bronze vessels (cylindricaltheca atramentaria, unguentaries, and aryballoi) werecharacterized in order to assess a correspondence betweenthe composition and the type of vessel and,possibly, to verify if these powders were inks or not.For the compositional characterization, a multi-analyticalapproach was adopted, which involved the use ofscanning electron microscopy–energy dispersive X-ray,Fourier-transformed infrared spectroscopy, Raman, X-raydiffraction, electron paramagnetic resonance spectroscopy,thermogravimetric analysis, gas chromatographycoupled with mass spectrometry (GC/MS), and pyrolysis GC/MS. Powders contained in cylindrical theca atramentariaform a homogeneous group, and their organic andinorganic compositions suggest that they were writinginks, while powders contained in unguentaries andaryballoi could have had several different uses, includingwriting inks and cosmetics. Furthermore, the compositionprofile of the powders found in cylindrical cases showsthat, at 79AD, in Pompeii, carbon-based inks were stillused for writing, and iron gall inks had not beenintroduced yet.
2011
- A round robin exercise in archaeometry: analysis of a blind sample reproducing a seventeenth century pharmaceutical ointment
[Articolo su rivista]
M. P., Colombini; F., Modugno; Gamberini, Maria Cristina; M., Rocchi; Baraldi, Cecilia; T., Deviese; R., Stacey; M., Orlandi; F., Saliu; C., Riedo; O., Chiantore; G., Sciutto; E., Catelli; L., Brambilla; L., Toniolo; C., Miliani; P., Rocchi; J., Bleton; U., Baumer; P., Dietemann; G., Pojana; S., Marras
abstract
Chemical analysis of ancient residues of pharmaceuticalor cosmetic preparations such as balms orointments is made problematic by the high complexity ofthese mixtures, composed of organic and inorganic materials.Consequently, a multi-analytical approach and specialcaution in the interpretation of the results are necessary. Inorder to contribute to the improvement of analyticalstrategies for the characterization of complex residues andto reconstruct ancient medical practices, a replica of a pharmaceutical formulation of the seventeenth century wasprepared in the laboratory according to a historicallydocumented recipe. In a round robin exercise, a portion ofthe preparation was analysed as a blind sample by 11laboratories using various analytical techniques. Theseincluded spectroscopic, chromatographic and mass spectrometricmethods. None of the laboratories was able tocompletely reconstruct the complex formulation, but eachof them gave partial positive results. The round robin exercise has demonstrated that the application of a multianalyticalapproach can permit a complete and reliablereconstruction of the composition. Finally, on the basis ofthe results, an analytical protocol for the study of residuesof ancient medical and pharmaceutical preparations hasbeen outlined.
2011
- Characterization of fresh and aged natural ingredients raw materials used in historical ointments by molecular spectroscopic techniques: IR, Raman and Fluorescence
[Articolo su rivista]
L., Brambilla; C., Riedo; Baraldi, Cecilia; A., Nevin; Gamberini, Maria Cristina; C., D’Andrea; O., Chiantore; S., Goidanich; L., Toniolo
abstract
Natural organic materials used to prepare pharmaceuticalmixtures including ointments and balsams havebeen characterized by a combined non-destructive spectroscopicanalytical approach. Three classes of materialswhich include vegetable oils (olive, almond and palm tree),gums (Arabic and Tragacanth) and beeswax are consideredin this study according to their widespread use reported inancient recipes. Micro-FTIR, micro-Raman and fluorescencespectroscopies have been applied to fresh and mildlythermally aged samples. Vibrational characterization ofthese organic compounds is reported together with tabulated frequencies, highlighting all spectral features and changes inspectra which occur following artificial aging. Synchronousfluorescence spectroscopy has been shown to be particularlyuseful for the assessment of changes in oils after aging;spectral difference between Tragacanth and Arabic gum couldbe due to variations in origin and processing of raw materials.Analysis of these materials using non-destructive spectroscopictechniques provided important analytical informationwhich could be used to guide further study.
2011
- Combined technique analysis on Punic cosmetic powders
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro
abstract
The Whitaker Museum in Mozia (Sicily) conserves some funerary vessels coming from the isle’s archaic necropolis. Greek, Phoenician and Etruscan amphorae, a rich collection of jars of Birgi necropolis and also materials coming from Mozia Tofet and houses are exposed. Also jewels and weapons, amulets, scarabs and objects with original inscriptions engraved are found, as well as cosmetic and surgical instruments and fragments of inscribed stones coming from the Lilibaeum necropolis. From the collection of the Mozia Museum 77 samples from an interesting variety of containers including Unguentaria, Balsamaria, Alabastra, pyxes and shell valves were taken. The powders found in this cosmetic vessels have been analyzed by using FT-IR, micro-Raman, SERS (Surface Enhanced Raman Spectroscopy) and XRF techniques and the results are reported in this work. The analyses carried out have shown the presence of a variety of compounds.The white powders, that are the more frequent ones, present in lead pyxes, were identified by micro-Raman as made of Cerussite PbCO3 coming from a complete carbonatation of hydrocerussite PbCO3*Pb(OH)2. This is compatible with the high chronology of the samples: instead, hydrocerussite has been identified in Pompeii samples. Its presence, confirmed by XRF measurements, can be a clear indication of cosmetic use, since it is well known that its use in mural painting is not advisable. At the time, cerussa (lead white) was employed as a foundation. Other white powders are mainly composed of calcite or aragonite: the first could come from the soil where the ancient founds were situated, the second one could derive from ground sea shells. Among white samples, but not only, TiO2 is frequently attested. Its presence should amount to the cosmetic use of ground rocks or could come from the Mozia soil, for example if ophiolites are available in the region.Litharge, an oxide present in many containers, could derive from the alteration of cerussa, or from a proper addition, whether the yellow colour had a special meaning for the population of the site. As to the yellow pigments a yellow ochre based on goethite was found together with lepidocrocite.Among the red pigments, beloved by Phoenician people, there are cinnabar and hematite: the latter can be found as a natural compound or as a thermodegradation product from goethite. The presence of red lead chromates crocoite and phoenicocroite, two rare minerals, in a particularly precious unguentary is a singular discovery.In one sample a trace of blue material was seen, that gave the spectrum of indigotine, a dye extracted in the past from many plants and used for dyeing tissues and in cosmesis.Among black materials carbon is one of the most frequently attested, alongside MnO2 (pyrolusite) and magnetite.Three samples analyzed exhibited red organic compounds, all fluorescent with normal Raman technique. By appliying a SERS technique it has been possible to record spectra relative to these red dyes, but till now, with a comparison of reference materials, it was only possible to exclude the common red such as madder, purple and kermes. Other comparisons are outstanding.In comparison with other sites, such as Pompeii, Herculaneum and Oplontis, this cosmetic powders showed a wider range of materials.
2011
- Spectral analysis of pharmaceutical formulations prepared according to ancient recipes in comparison with old museum remains
[Articolo su rivista]
Gamberini, Maria Cristina; Baraldi, Cecilia; Freguglia, Giada; Baraldi, Pietro
abstract
A study of the composition of the remains ofancient ointments from museums was undertaken to enableunderstanding of the preparation techniques. Comparison ofancient recipes from different historical periods andspectroscopic characteristics of inorganic and/or organicremains recovered in museum vessels enabled preparationof ancient pharmaceutical–cosmetic formulations. FarmacopeaAugustana by Occo was one the most importantbooks studied for the 14 formulations prepared in thelaboratory. Three formulations are discussed in detail andraw materials and new preparations were proposed forozone ageing. The most important micro Raman results arediscussed. The spectra of the raw materials lipids, beeswax,and resins are discussed; beeswax and pig suet (axŭngia)Raman spectra were found to be similar, but different fromthose of the aged oils. SERS was applied to ancientointments and galbanum and the Raman spectra arereported and discussed for the first time.
2011
- The Officina Pigmentaria in Pompei: pigments and cosmetics
[Relazione in Atti di Convegno]
Baraldi, Pietro; S., Petrullo; Baraldi, Cecilia; G., Trojsi; A., Varone
abstract
According to the “Giornale di Scavo” of the Archaeological Superintendance of Pompeii, the first excavation in the Regio I, Insula 9 (I,9,9) took place in 1952. In a building of seven rooms there was a stair in opus incertum with the floors in cocciopesto. Near the skeletons of four individuals, about 150 globular bowls, fritilla and ollae were found. They were assigned the numbers between 9389 and 9700. Due to the high number of containers and to the presence of material inside, they have a high importance for the history of materials in Pompeii and in the Roman world. In particular, they should be important for the reconstruction of the painting history and techniques of this period. An investigation with different techniques for the identification of the contents composition and subsequently for the understanding of the materials present was then undertaken. For the study two molecular techniques were used, that is FT-IR spectroscopy and Raman microscopy. The first is able to supply information about the general composition of the compound present in the samples at least in the concentration of about 1 %. The second techniques can inform on the composition of single grains as small as 1-2 micrometers. Therefore, the results of the two techniques must help each other to understand what the analyzed powder is. The analyses of all the bowl contents are summarized in a long table, of which we report only a section. By comparing the results obtained some considerations come to light. Many containers have quartz and calcite, that are the main component of plasters, to which feldspars and pyrite can be added. At the same time diopside can come from eruptive rocks or from silicate materials heated to high temperature. Aragonite is present, sometimes at high concentration, in many pigments, and its presence can be due to natural provenance from white minerals, but more probably can be due to the grinding of shells. This is an important testimony of what is identified in white lines on colored background in Roman wall paintings. The blue pigment is always based on Egyptian blue, at the time of Pompeii destruction coming from Puteoli or Liternum. Green can be obtained by mixing a yellow and a blue, and this is generally found on wall paintings; more frequently green is ascertained to be a mixture of green earth and some Egyptian blue. Malachite and azurite are encountered as degradation products of copper and brass containers. Other rare occurrence are cuprite, also coming from alterations of a metal, and litharge, from alteration of cerussite or lead objects. The case of cerussite or hydrocerussite is different. It can be identified in many recipients, but it is not a pigment for wall paintings. Since it is known from Pliny and other authors that it was used as a fard, this can be a proof of the production and filling also of cosmetics containers in I, 9, 9.
2010
- Auctoribus curae fuere lapides mortariorum quoque nec medicinalium tantum aut ad pigmenta pertinentium (Pliny 36, 43). Our authors are interested in stones, for making mortars, and not only in officinal mortars or those uded for colors.
[Relazione in Atti di Convegno]
Baraldi, Pietro; Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina
abstract
A very important phase for reconstructing ancient technology and human activities is the analisys of artifacts. It can supply a lot of information, but sometimes the data obtained are not understandable. On the other hand an amount of written information is available since the classical antiquity. Some of the authors are considered not to be scientist and therefore their data are neither used nor interpreted. Beyond published texts some unpublished manuscripts are known that could be very interesting. Other documents include ancient translations from other languages, such as the Greek papyrii, and the Arabian documents from Spain, documents regarding trade and history of countries, icones in ancient paintings, tools used for paintings and other activities. In more recent time it is to recall, the "secreti", the books for treating diseases, where the subjects not only concern madicine, but include preparation of pigments, dyes, lakes, cosmetics, alloys inks...Their contents can be very old, some being composed much before Christ and re-written many times, and translated and sometimes erroneusly read. The transcription, understanding and interpretationof these recipes can help in understanding: the ancient paintings, decorations, alloys, textiles and cosmetics; the presence of some compounds as a consequence of past treatments and restorations; the survival of some compounds not necessary for the formulate, but added for somo forgotten reasons, such as folklore, superstition, faith, magic; the degradation of somo parts of artworks due to time and environment.These items have been followed in examining and unpublished miscellanea from the Biblioteca Estense Universitaria in Modena.
2010
- COSMETIC AND PHARMACEUTICAL FORMULATIONS: FROM PAST TO PRESENT
[Relazione in Atti di Convegno]
Gamberini, Maria Cristina; Freguglia, Giada; Baraldi, Cecilia; Baraldi, Pietro
abstract
The interest devoted to the scientific treatment of analytical data obtained from ancient founds preserved in Italian and foreign institutions and Museums is nowadays relevant. However, till now the study of the composition and the understanding of the preparation technologies of ancient founds is scanty and fragmentary. Now, the progress of instrumental techniques enables the material composition to be cleared in details and to advance a possible re-proposition of the handiworks. On the basis of analytical data, the possibility to establish the nature of raw materials and the formulations, becomes even more concrete.In the framework of the PRIN project the unit of Modena has thrown the basis for the study of ancient cosmetic, medical and pictorial founds, in particular: 1)Identification and sampling of ancient remains in national and international Museums and of handiworks not purely cosmetic or medical.2)Spectroscopic studies (FT-IR, micro-Raman and XRF) for the characterisation of inorganic and/or organic remains recovered in unguentaries and in containers of ancient workshops.3)Identification and study of the ancient published and unpublished bibliographic sources: translation from Latin and vernacular followed by an interpretation of the function of raw materials. 4)Identification in the actual market of the materials used in antiquity.5)Preparation or acquirement of raw materials not available on the market.6)Reproduction in a modern perspective of ancient formulations on the basis of the ancient sources. The first step faced was the acquirement of ancient founds, that is the sampling on the spot of samples to be studied. Therefore, samples were taken at the Museum Aboca (Sansepolcro, Arezzo). At the Aboca Museum about 68 pots were inspected and 30 exhibited a fair amount of residue of which 9 were the object of the study.After sampling, the materials were analysed by Micro-Raman and FT-IR in order to have a first screening of them, that is to determine whether they were of organic or inorganic origin and which compounds were present. In this way we got a first idea of what the materials were. Thanks to the spectroscopic analyses and to the labels on the containers, we proceeded into the research of ancient similar formulations. Therefore, it was necessary to examine the recipe books starting from the classical age till to the beginning of scientific chemistry and pharmacology in order to critically compare the materials found, to understand their nature, their possible alteration undergone with time, the novelties in comparison with preceding versions, the technological acquirements of an age in comparison with the others. From the study of the inscriptions reported on the containers and the interpretations carried out, the period of actualisation of the formulation was hypothesised. The study of the same formulation in subsequent times has shown the evolution and the adaptation to the age.Many ancient books and manuscripts reporting recipes concerning the subject in the period between 1597 and 1872 have been considered, the most interesting of these was Farmacopea Augustana by Occo, 1597. For each source, the desired recipes were searched for and then, if necessary, translated and interpreted. In fact, some texts are in Latin or vernacular (Farmacopea Augustana by Occo), French (Abrégé de Matière médicale et de Thérapeutique by C. Binz) or Spanish (Farmacopea Hispanica), and the translation must be careful, since the meaning of the terms at the time was searched 1-7.The next step was to study the raw materials used in the recipes, that is to verify the persistence of the ingredients today and their availability in commerce. The ointments to be prepared were chosen as a function of the remains found in the containers, but mainly on the basis of the results of the spectroscopic analyses. Those reproduced in the laboratory were many, sometimes the preparations have been ma
2010
- Color traces and their identification in paintings, cosmetics, writings
[Abstract in Atti di Convegno]
Baraldi, Pietro; Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Ansaloni, Ivano
abstract
During the last years of research carried out on the basis of a financial support by MIUR, many samples have been encountered of different nature, colour, origin and physical state. In examining containers present in the Italian Archaeological depositories and Museums, we have found or we were adviced of interesting coloured materials and we were asked to identify them.The identification is sometimes rich of information about the ancient technology for preparing elaborated formulates, such as cosmetics, drugs, ointments, perfumes, pigments, lakes, dyes. Thereby, their analysis enables important passages of the production to be understood and some literary sourced to be interpreted. In examining some materials present on bones due to particular rituals of the first centuries after Christ in Aemilia, a particular identification of manganese based materials was encountered. The presence of manganese oxides can be related to the geology of the Aemilian territory. However, similar compounds are present in Etruscan tiles decorated with Egyptian blue and other pigments in Marzabotto. This fact supply information on the commerce of Egyptian blue far before Roman Empire times and the passage of manganese oxide treatment for painting to subsequent cicilizations.The necessity for ancient populations to paint testimonies of past religious or military chiefs lead to a search for materials coming from far centuries, such as Baltic amber, Egyptian blue, indigo… In places with an always more ancient chronology, such as Verucchio Aemilia, these materials are found in large amounts. It is not clear whether indigo was extracted from Isatis tinctoria or an Indigofera.Traces of saffron and indigotine on fictile antefissae in Cuma testifies the use of re-painting the artefacts every while, as a sign of respect for the temples. Ancient colored lipsticks contain pink ingredients, that may be purpurissum, but could be also the cheaper purpurissum puteolanum, as revealed by SERS analysis of Pompeiian samples.Residuals of precious materials are found also in small containers of the Roman ages. Smal traces of gold an a black preparation identify the knowledge of a gilding technique on alabaster, whit the black assisa applied on small spots. The ensemble of materials and their use enable an amount of knowledge to be supposed in ancient populations in order to make their life more comfortable and elegant.
2010
- MULTI ANALITYCAL APPROACH TO AGED COMPLEX MATRICES
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro; M. P., Colombini
abstract
Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds. At present some founds from pharmacies of Italy (Genua, Sansepolcro) and Spain (Majorca) amounting to the XVII century and Egyptian ointments of the II millennium b.C. from the Turin Museum are under study.The analysis protocol provides firstly non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, were identified as the most suitable techniques for a first approach to the analysis of the ancient samples. Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. In this study are reported some data about the composition of some ancient Egyptian samples. It can be observed that Titanite is present, a mineral possibly coming from mines in Southern Egypt.Concerning to organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability like the natural products, in addiction there are the ageing and the degradation process that make very difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available.Some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gum arabic, gum tragacanth), animal fats and waxes commonly employed in the ancient preparations. On the basis of the examination and critical interpretation of ancient literature sources (pharmacopoeias) fifteen samples based on pharmaceutical and cosmetic recipes were prepared as a reference samples. The raw materials and thereference formulations were artificially aged by using heating (in a oven at 60°C for 1 month), photo-oxidation (with ozone for 20 hours) and enzymatic degradation (by means of a pool of cellulase, lipase and laccase).Concerning the raw materials, only few showed fluorescence in Raman microscopy, but this decreases sharply with the artificial ageing process. This fact could be due to the loss of fluorophores.The artificial ageing produces different alterations according to the type of ageing. Among the first results we reported the analysis of Pompeii sample already identified as palm oil by GC-MS2. The comparison with our database showed correspondence with palm oil enzymatically degraded. This indicates that this database is interesting in recognising the organic materials into archaeological holders.
2010
- Multianalytical approach to aged complex matrices
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro
abstract
Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds. At present some founds from pharmacies of Italy (Genua, Sansepolcro) and Spain (Majorca) amounting to the XVII century and Egyptian ointments of the II millennium b.C. from the Turin Museum are under study. The analysis protocol provides firstly non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. These measurements involve other research groups of our project supported by a national Fund (PRIN: Colours and ointments in antiquity). We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, were identified as the most suitable techniques for a first approach to the analysis of the ancient samples. Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. Concerning the organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability like the natural products, in addiction there are the ageing and the degradation process that make very difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available.Some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gum arabic, gum tragacanth), animal fats and waxes commonly employed in the ancient preparations. On the basis of the examination and critical interpretation of ancient literature sources (pharmacopoeias) fifteen samples based on pharmaceutical and cosmetic recipes were prepared as a reference samples. The raw materials and the reference formulations were artificially aged by using heating (in a oven at 60°C for 1 month), photo-oxidation (with ozone for 20 hours) and enzymatic degradation (by means of a pool of cellulase, lipase and laccase).Concerning the raw materials, only few showed fluorescence in Raman microscopy, but this decreases sharply with the artificial ageing process. This fact could be due to the loss of fluorophores. The artificial ageing produces different alterations according to the type of ageing. Among the first results we reported the analysis of Pompeii sample already identified as palm oil by GC-MS2. The comparison with our database showed correspondence with palm oil enzymatically degraded. This indicates that this database is interesting in recognising the organic materials associated to archaeological founds.
2010
- MultyAnalytical Approach to Aged complex Matrices
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro; M. P., Colombini
abstract
Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds. At present some founds from pharmacies of Italy (Genua, Sansepolcro) and Spain (Majorca) amounting to the XVII century and Egyptian ointments of the II millennium b.C. from the Turin Museum are under study.The analysis protocol provides firstly non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. These measurements involve other research groups of our project supported by a national Fund (PRIN: Colours and ointments in antiquity). We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, were identified as the most suitable techniques for a first approach to the analysis of the ancient samples. Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices4. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. In Tab.1 are reported some data about the composition of some ancient Egyptian samples. It can be observed that Titanite is present, a mineral possibly coming from mines in Southern Egypt. Concerning to organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability like the natural products, in addiction there are the ageing and the degradation process that make very difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available.Some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gum arabic, gum tragacanth), animal fats and waxes commonly employed in the ancient preparations. On the basis of the examination and critical interpretation of ancient literature sources (pharmacopoeias) fifteen samples based on pharmaceutical and cosmetic recipes were prepared as a reference samples. The raw materials and the reference formulations were artificially aged by using heating (in a oven at 60°C for 1 month), photo-oxidation (with ozone for 20 hours) and enzymatic degradation (by means of a pool of cellulase, lipase and laccase).Concerning the raw materials, only few showed fluorescence in Raman microscopy, but this decreases sharply with the artificial ageing process. This fact could be due to the loss of fluorophores. The artificial ageing produces different alterations according to the type of ageing. Among the first results we reported the analysis of Pompeii sample already identified as palm oil by GC-MS2. The comparison with our database showed correspondence with palm oil enzymatically degraded. This indicates that this database is interesting in recognising the organic materials into archaeological holders.
2010
- RAMAN TECHNIQUES APPLIED TO ANCIENT COSMETIC AND PHARMACEUTICAL PREPARATIONS
[Relazione in Atti di Convegno]
Baraldi, Cecilia; Gamberini, Maria Cristina; Freguglia, Giada; Baraldi, Pietro
abstract
Complementary spectroscopic techniques, such as FT-IR and Micro-Raman spectroscopies are valuable means for maximizing the amount of information provided by complex matrices like the remains in archaeological containers. The difficulty in analyzing archaeological samples is due to their composition which generally involves a mixture of different inorganic and organic materials, some times degraded by the environmental conditions. We report the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory, of a first approach to the analysis of the ancient samples. The analytical results showed the importance of micro-Raman Spectroscopy in discriminating between inorganic and organic materials, thereby underlining the complexity of pharmaceutical and cosmetic matrices.Raman microscopy is the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices. On the basis of the FT-IR and micro-Raman spectra, it was possible to identify some specific old cosmetic materials and some binders used in cosmetic preparations. In particular, Raman microscopy was able to identify the presence of constituents at the trace levels or compounds having vibrations at low wavenumbers within the sample examined, that it is not possible with normal FT-IR technique. This technique can easily identify compounds like lead oxide, red lead, cinnabar, rare minerals, (etc.) that could give interesting information about the original composition of the formulate and the provenance of the raw materials.Concerning the organic materials, their possibility of identification is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples are subjected to ageing and degradation process that make difficult to recognize the raw material originally present. For understanding the possible changes undergone by materials during ageing, a specific database of spectra must be available.In the project PRIN 2007 “Colours and balms in antiquity” some thirty raw materials were chosen among oils (e.g. olive, almond, and palm oil), gums (e.g. gumarabic), animal fats and waxes, commonly employed in the ancient preparations. The raw materials and the reference formulations prepared in the laboratory, were artificially aged. The reference Raman spectra have supplied an interesting database.The use of Surface-Enhanced Raman Spectroscopy (SERS) enabled to increase Raman signal and to decrease the background fluorescence for some samples. This techniques exhibits new perspectives for the study of organic and inorganic compounds in the field of cultural heritage.
2010
- STUDY AND PREPARATION OF ANCIENT COSMETIC AND PHARMACEUTICAL FORMULATIONS IN A PRESENT PRESPECTIVE
[Abstract in Atti di Convegno]
Freguglia, Giada; Baraldi, Cecilia; Gamberini, Maria Cristina; Baraldi, Pietro
abstract
The study of ancient cosmetic and pharmaceutical formulations involved the examination of several recipe books starting from the classical age till to the beginning of scientific chemistry and pharmacology. The study of the same formulation in subsequent times has shown the evolution and the adaptation to the age. Many ancient books and manuscripts reporting recipes concerning the subject in the period between 1597 and 1872 have been considered. Study of the ancient remains found inside unguentaries and of the raw materials used in the recipes has been necessary. Not all the raw materials could be bought, some needed to be prepared in the laboratory, such as the rose-water and the turnip juice, two ingredients used in the preparation of many ointments.The ointments to be prepared were chosen as a function of the remains found in the containers, but mainly on the basis of the analytical results coming out from ancient remains analysis. Those reproduced in the laboratory were many, sometimes the preparations have been made in double or triple, according to the sources of different historical periods. The total number of the ointments reproduced was fourteen.
2010
- STUDY OF ANCIENT PHOENICIAN REMAINS
[Abstract in Atti di Convegno]
Freguglia, Giada; Baraldi, Cecilia; Gamberini, Maria Cristina; P., Toti; Baraldi, Pietro
abstract
The Mozia Museum conserves some funerary vessels coming from the isle’s archaic necropolis, commercial Greek, Phoenician and Etruscan amphorae, a rich collection of black varnish jars with red images of Birgi necropolis and also materials coming from Mozia Tofet and houses. Also jewels and weapons, amulets, scarabs and objects with original captions engraved are found, as well as cosmetic and surgical instruments and fragments of inscribed stones coming from the Lilibeo necropolis. From the collection of the Mozia Museum about 200 samples from the Unguentaria and Balsamaria were taken, some having large amount of residue, others a very small one. A preliminary spectroscopic analysis was carried out on these samples by using Micro-Raman and SERS techniques and the results of a first series are reported in this study. The preliminary analyses carried out with the Raman techniques have shown the presence of a variety of compounds.The white powders, among the more abundant ones, present in lead pyxes, were made of Cerussite PbCO3 coming from a complete carbonatation of hydrocerussite PbCO3*Pb(OH)2. This is compatible with the high chronology of the samples: instead, hydrocerussite has been identified in Pompeii samples. Its presence can be a clear indicator of cosmesis, since it is well known that its use in mural painting is not advisable. At the time, cerussa (lead white) was employed as a foundation. Other white substances are calcite and aragonite: the first could come from the ground where the unguentaria were found, the second one could derive from ground sea shells.Litharge, an oxide present in many containers, could derive from the alteration of cerussa, or from a proper addition, whether the yellow colour had a special meaning for the population of the site.The container NI 3149 had a gray powder composed of Carbon mixed with calcium phosphate. This could have been a bone-black or could come from cinerary urn.Among the red pigments found there are cinnabar and hematite: the latter can be found as a natural compound or as a thermodegradation product from goethite. The presence of red lead chromates crocoite and phoenicocroite, two rare minerals, in a particularly precious unguentary is a singular discovery.With the SERS technique it has been possible to record spectra relative to red dyes. However, these spectra do not correpond to compounds coming from madder, purple and kermes. Other comparisons are outstanding. In comparison with other sites, such as Pompeii, Herculaneum and Oplontis, this cosmetic powders exhibit a wider range of materials.
2010
- Spectroscopic Characterization Of Ancient Matrices
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; Baraldi, Pietro; M. P., Colombini; O., Chiantore
abstract
Since a decade our research group deals with the analysis of ancient cosmetics and drugs, starting from the Roman founds 1-3. Actually, this kind of study involves other research groups supported by a national Fund (PRIN: Colours and ointments in antiquity). Firstly the analysis protocol provides non-destructive analyses and then the more expensive and destructive analyses, such as gas-chromatography-mass spectrometry (GC-MS) methods. The samples analyzed in this study were collected from the Egyptian Museum of Turin, Italy. The discovery of the studied archaeological finds was made by Ernesto Schiaparelli (1906 until 1913) and the archaeological founds were dated from the late III millenium b.C. to early II millenium b.C. The sites of finding were in Assiut (at about 400 Km from Cairo on the bank of the Nile) and Gebelein (south of Assiut), near the southern border with Nubia. In the sarcophagus usually it is possible to find weapons, like bows and arrows, textiles and also ointments. Here the results of the vibrational spectroscopy techniques, such as Raman microscopy (laser 632 nm), FT-Raman spectroscopy (laser 1064 nm) and FT-IR/ATR with a golden gate accessory are reported. These techniques are identified as the most suitable ones for the first approach to ancient samples analysis. Raman microscopy is in fact the most suitable technique in order to identify minor inorganic components and contaminants at the micrometric scale inside these complex matrices4. This technique can easily identify compounds like lead oxide, vermillion, rare minerals, (etc.) that could give interesting informations about the provenance of the raw materials and the original composition of the formulate. In the present study some data are reported concerning the composition of five ancient Egyptian samples. It can be observed that Titanite is present, a mineral possibly coming from mines in Southern Egypt5.Concerning to organic materials, their possibility of identification, is very different from that of inorganic ones. Some compounds were rapidly degraded, some others persisted till to present day, often unchanged (e.g. wax). Historical samples give a chemical variability due to the natural products, in addiction, ageing and degradation processes make very difficult to recognize raw materials originally present. For understanding the possible changes undergone by materials in ageing, a specific database of spectra must be available. Some thirty raw materials were chosen among oils, gums, animal fats and waxes commonly employed in the ancient preparations. The reference materials were in laboratory artificially aged by heating, photo-oxidation and enzymatic degradation. Some artificial materials aged produced different alterations according to the type of ageing. The comparison to one remain sample and our database spectrum showed a correspondence with the enzymatically degraded palm oil spectrum. This indicates the importance of this database in recognising the organic materials into archaeological holders.
2010
- Studio di preparati farmaceutici del XVIII-XIX secolo tramite GC/MS e HPLC-DAD
[Relazione in Atti di Convegno]
M., Rocchi; E., Ribechini; I., Degano; F., Modugno; Gamberini, Maria Cristina; Baraldi, Cecilia; M. P., Colombini
abstract
Il presente lavoro è volto allo studio e alla conoscenza chimica delle sostanze organiche naturali impiegate nella realizzazione di antichi preparati farmaceutici. Questa ricerca è stata svolta nell'ambito del progetto nazionale PRIN07 dal titolo "Colori e balsami nell'antichità: dallo studio chimico alla conoscenza delle tecnologie in cosmesi, pittura e medicina". In questa sede verranno mostrati i risultati ottenuti dallo studio di preparati antichi provenienti dal Museo di Aboca di S. Sepolcro (AR), della Real Cartuja de Valdemossa (Palma di Maiorca) e del Museo di S. Agostino (Palazzo Tursi, GE). A causa della complessità della composizione chinica delle matrici sono state scelte per l'analisi della componente organica tecniche cromatografiche e in particolare la gas cromatografia accoppiata alla spettrometria di massa (GC/MS) e la cromatografia liquida ad alta pressione con rivelatore a serie di diodi (HPLC-DAD). Queste tecniche permettono la separazione e l'identificazione delle singole specie chimiche presenti e tra queste il riconoscimento di markers bio-molecolari. La combinazione dei dati ricavati dalle analisi di sostanze naturali sottoposte a invecchiamento, di unguenti riformulati seguendo ricettari e documenti d'epoca hanno permesso la caratterizzazione delle sostanze prese in esame e a migliorare la conoscenza della farmacopea antica. La presenza di diverse classi di composti, in particolare di acidi grassi mono- e poliinsaturi a catena corta e a catena lunga, diacidi, idrossiacidi, alcol a catena lunga, n-alcani a catena lunga e acidi diterpenoidi hanno evidenziato tre diversi tipi di sostanze: cera d'api, olio vegetale e resina di pino.
2010
- Vibrational Study of Propantheline Bromide Polymorphism
[Abstract in Atti di Convegno]
Baraldi, Cecilia; Freguglia, Giada; Gamberini, Maria Cristina; A., Tinti
abstract
Propantheline or 2-Propanaminium, N-methyl-N-(1-methylethyl)-N-[2-[(9H-xanthen-9-ylcarbonyl)oxy]ethyl]- bromide is a quaternary ammonium synthetic derivate with modulation activity on vagal tone. It is one of the most parasympatholytic active agent with peripheral activity similar to atropine. It reduces the hypersecretion and the ipermotility of the gastro-intestinal apparatus and it has spasmolitic properties. The presence of two known Propanteline bromide polymorphs is reported in literature1,2: the stable form I and the metastable form II. Through multi-analytical approach used by our group in other pholimorphic studies, in the present communication we report the study and characterization of the studied two forms. For the first time micro-Raman spectroscopy and Hot-Stage Raman microscopy (HSRM) studies of Propantheline polymorphs are reported. Raman techniques were useful tools for distinguish and monitor the conversion of polymorphs cause of changing temperature. The spectroscopic reported data, together with those form previous reports, complete the Propantheline bromide polymorphs knowledge. DSC thermograms and X-Ray powder diffraction data, were also collected. Furthermore XRPD patterns of I and II forms were in agreement with Kountourellis data. Some attributions of significant IR and Raman bands were firstly reported. In summary, the IR spectra permitted to identify I and II polymorphs through their typical bands at 1729, 1250-1235, 1171-1157, 1038, 758-746, 713, 630 cm-1 and 1727-1739, 1260, 1166, 1032, 753-744, 709 cm-1, respectively. The polymorphs characterization through Raman spectroscopy permitted to identify specific bands for form I (1267-1255, 1222, 520, 417-402-380, 294, 255 cm-1) and form II (in particular at 1229, 669, 537-530, 397, 295-282 and 185 cm-1).According to L. Borka results1,6, in this study a conversion of II into I form was observed. The conversion occurred above 100°C with a successive fusion of I form. A further heating caused a decomposition phenomenon. The used temperature program started form 35° until 200°C with an heating rate of 2°C/min. To confirm DSC results of form II, Hot-stage measurements were carried out with the same DSC temperature program (2°C/min; 35-200°C temperature range). By this technique, the same results recovered with DSC thermal curves were noticed: a conversion of II into I form was observed and the successively fusion phenomenon was noticed. At 35°C until 80°C, the micro-Raman spectra correspond to form II, while at 90°C and at 160°C the transformation into I and its melting event were occurred, respectively.Moreover, the thermodynamic and spectroscopic behaviour of ground form I was investigated. Propantheline form I was ground at different times (1, 5, 10, 15, 20 minutes) and FT-IR/ATR and DSC measurements were carried out. In addition, a certain amount of recrystallized Propantheline bromide (form I, II) was placed into a compressing machine to obtain Propantheline bromide tablets using different compression forces (2, 4, 8, 10, 12, 16 and 28 KN). Using Raman microscopy, surfaces and inside tablets studies were carried out for verifying the polymorphic transformations. Polymorphic transformations were not been induced.
2009
- As beautiful as the woman in Ancient Rome : an overview of the Raman studies on cosmetic powders from Pompeii
[Abstract in Atti di Convegno]
E., Van Elslande; Gamberini, Maria Cristina; Baraldi, Cecilia; P., Walter
abstract
White for the face, black for the eyes and red for the lips and the cheeks, there are the principal colours used by the women of the ancient Mediterranean world to makeup themselves, as confirmed by the description of the habits given by Ovid1 or Tertullian2. But what about the materials used? A multi-analytical approach for the study of cosmetics samples from the ancient Greek and Roman worlds enlighted us about the diversity of materials used3,4.We propose here to focus on Raman and SERS results obtained on pompeian samples to show the complexity of the formulation of roman cosmetic powders.
2009
- Vibrational study of acetazolamide polymorphism
[Articolo su rivista]
Baraldi, Cecilia; Gamberini, Maria Cristina; A., Tinti; Palazzoli, Federica; Ferioli, Valeria
abstract
In this paper, an acetazolamide vibrational study has been conducted to identify its two known polymorphic forms (A and B). Other techniques, such as Hot-stage and X-ray powder diffraction, have been also reported. Moreover, the thermodynamic and spectroscopic behaviour of ground form A has been investigated.In this study, acetazolamide form A was ground at different times (1, 5, 10, 15, 20 min) and FT-IR/ATR and DSC measurements have been carried out. The grinding process, decreasing the particle sizes, has been induced a polymorphic transformation of A to B form.To determine the B in A percentages, calibration curves have been performed by FT-Raman measurements.
2008
- AN INTEGRATED ANALYTICAL APPROACH FOR CHARACTERIZING AN ORGANIC RESIDUE FROM AN ARCHAEOLOGICAL GLASS BOTTLE RECOVERED IN POMPEII (NAPLES, ITALY)
[Articolo su rivista]
F., Modugno; E., Ribechini; Baraldi, Cecilia; Baraldi, Pietro; M. P., Colombini
abstract
Within the framework of an Italian research project aimed at studying organic residues found in archaeological objects from the Roman period, the chemical composition of the contents of several glass vessels recovered from archaeological sites from the Vesuvian area (Naples, Italy) was investigated.In particular, this paper deals with the study of an organic material found in a glass bottle from the archaeological site of Pompeii using a multi-analytical approach, including FT-IR, direct exposure mass spectrometry (DE-MS) and GC–MS techniques.The overall results suggest the occurrence of a lipid material of vegetable origin. The hypothesis that the native lipid material had been subjected to a chemical transformation procedure before being used is presented and discussed.
2008
- Libro di Vari Secreti
[Concordanza]
Baraldi, Cecilia; Baraldi, Pietro; F., Paccagnella
abstract
Il manoscritto cartaceo D/XI/20 a firma di Francesco Pinelli è una miscellanea di indicazioni per vari tipi di operazioni: contiene ricette tra le quali alcune sono indicate come copiate da qualche testo precedente. Le dimensioni sono di 175 x 140 mm. Pur essendo del primo Settecento, appare interessante in quanto contiene la descrizione di numerose modalità di esecuzione di dorature e argentature, di tempere di metalli, di saldature, di preparazione di smalti, specchi, colle, vernici e leghe. Sono da rilevare anche ricette per la preparazione di alcuni colori, inchiostri, sali, acquaforte. Un piccolo trattato di alchimia ad opera di un medico di nome Giovanni Filomani e inserito interamente riportando il linguaggio usuale della materia di quel tempo. Vengono ricordati tra l’altro Raimondo e Arnaldo che sono chiaramente da identificarsi in Raimondo Lullo e Arnaldo di Villanova, due celebri alchimisti. Un terzo nome riportato, Elmoncio, sembra quello di van Helmonth (1577-1644), lo scopritore dell’acido cloridrico, alchimista e medico.Numerosi simboli per gli elementi, metalli e composti sono rappresentati e riassunti in una tavola alla fine del testo che prende tre pagine successive (vedi foto sotto). Vengono citati anche tre termini di origine alchemica: devenec che può raffrontarsi al duhenec o duenech dei testi alchemici (G. Testi, Dizionario di Alchimia e di Chimica Antiquaria, Ed. Mediterranee Roma 1980), azoqueh, mercurio e alchaesth, preparato a base di mercurio.
2008
- MicroRaman and infrared spectroscopic characterization of ancient cosmetics
[Articolo su rivista]
Gamberini, Maria Cristina; Baraldi, Cecilia; Palazzoli, Federica; E., Ribechini; Baraldi, Pietro
abstract
By FT-IR and microRaman spectrometry a large number of black to gray powders have been analysed. The studied remains were found inside Pompeiian unguentaries situated in depository of ‘‘Casa Bacco’’. By the analytical results it has been possible to understand the different nature and composition of the materials employed in preparation of ancient cosmetic powders. Dark black powders were essentially composed of amorphous carbon probably due to the carbonisation of vegetal or animal tissues. By using different starting materials or by adding different powders to the black carbon other hues could be also obtained. Particularly, this study enabled to gain a complete and unambiguous composition characterization of these old cosmetics.
2007
- A Raman study of white cosmetics from the classic world
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Cecilia; Palazzoli, Federica; P., Walther; Baraldi, Pietro
abstract
Some samples coming from different regions of the ancient Mediterranean World have been studied by Raman microscopy. The powders were apparently white cosmetics used in female contexts. A detailed analysis of their FT-IR and Raman spectra revealed that many compounds were present.Fluorite, apatite, sodium nitrate; pyrolusite, lead white, quartz, indigo, black cuprite, gypsum, goethite, have been identified. The presence of so many different and coloured compounds can help in the description of the preparation method used at the time by the artisans and to understand the changes intervened due to chemical alterations and degradation in the course of time. Perhaps different technologies to obtain white cosmetics were used, depending on local availability of materials and social levels of buyers. Traces of binders are sometimes detectable by infrared spectroscopy.
2007
- A micro-Raman archaeometric approach to Roman wall paintings
[Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; R., Curina; Tassi, Lorenzo; Zannini, Paolo
abstract
Infrared and Raman spectra have been recorded on the surface of plasters from Regium Lepidi (Reggio Emilia, Italy). A palette has been identified, that can be compared with the ones from the nearby towns of the Roman Empire, but some peculiarities can be outlined. Some of the pigments could come from the territory, even though the techniques could be ascribed to those usually present in the 1st century a.c.
2007
- Black eyeliners in ancient Rome: the case of Pompeii
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Baraldi, Cecilia; Palazzoli, Federica; E., Ribechini; Baraldi, Pietro; P., Walter
abstract
Many of the ancient black eye paints, the kohls, consisted of galena, stibine or antimony sulfide, cerussite and in addition laurionite and phosgenite as reported by other authors. The Roman civilization made of their own this type of Egyptian cosmetic, moreover the literature reports also the use of the simplest and cheapest fuligo (black smoke) used to mark the eyebrows and the contour of the eyelashes. A large number of black-to-grey powders found inside Pompeiian unguentaries have been analysed by infrared spectrometry and Raman microscopy. The analyses show that deep black powders are essentially amorphous carbon that can derive from the carbonisation of vegetal or, frequently, animal tissues. In fact, carbon is found to be associated with apatite, whose presence could be attributed to the carbonisation of animal bones in a controlled atmosphere. Concerning the gray powders it is also to underline the rare occurrence of some particular materials that have been detected in painting materials (“Casa dei Casti Amanti” and the “Officina pigmentaria”); among them it is to recall jarosite, a yellow basic iron sulphate already identified in Egyptian paintings.Other interesting findings are anglesite and epsomite, not ascribable to the existence on the site of minerals of this kind: they can be interpreted as degradation products of other materials, such as magnesite, dolomite and cerussa, in the presence of sulfur dioxide from the surges or from the modern acid rains.The rare occurrence of minium could be bound to the use as a pinkish material for fards or to a degradation due to heating of cerussa during the violent surges of the 79 a.C. The presence of the iron classes of compounds (hematite, goethite, lepidocrocite and magnetite) could derive in some cases from a proper addition of an ochre, in order to obtain a special nuance of fard. The occurrence of aragonite and dolomite is parallel to the analogous findings among the painting materials, whereas cerussite comes from a carbonatation of hydrocerussite, the proper component of cerussa, the preeminent ancient white cosmetic used as foundation cream.
2007
- Chemical composition and characterisation of seeds from two varieties (pure and hybrid) of Aesculus hippocastanum
[Articolo su rivista]
Baraldi, Cecilia; Bodecchi, Lidia Maria; Cocchi, Marina; Durante, Caterina; Ferrari, Giorgia; Foca, Giorgia; Grandi, Margherita; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Investigations have been conducted on some samples of naturally desiccated horse-chestnuts (Aesculus hippocastanum), representativeof the two most common mediterranean varieties: the pure species (AHP, giving white flowers), and a hybrid (AHH, giving pink flowers).Different experimental techniques have been used to gain more information on morphological structure and chemical composition ofthese complex matrices. Surface analysis by SEM showed no differences in such floured samples (wild type), while thermal behaviour(DSC) outlines some significant differences between them. Chemical composition reveals some differences in residual moisture(AHP = 6.97%; AHH = 6.59%), proteins (AHP = 2.64%; AHH = 1.82%), lipids (AHP = 4.13%; AHH = 5.10%), glucides (AHP =15.2%; AHH = 14.3%), and ashes (AHP = 2.51%; AHH = 2.19%). Most likely, these characters modulate other undifferentiated chemicalparameters, such as cold water solubility (CWS:AHP = 53.9%; AHH = 48.6%), and total inorganic soluble salts (TISS:AHP = 2.18%; AHH = 1.92%). Principal component analysis was applied to differentiate the two horse-chestnuts varieties. In particular,the first principal component effectively distinguish and discriminates AHH and AHP samples in two well-separated categories, giving, atthe same time, some information on the influence of the whole set of chemical compositional parameters.
2007
- Colour fading in textiles: A model study on the decomposition of natural dyes
[Articolo su rivista]
COLOMBINI M., P; Andreotti, A; Baraldi, Cecilia; Degano, I; Luceiko, J. J.
abstract
This paper describes an analytical procedure based on GC-MS to identify in textiles the most common flavonoid yellow dyes used in Europe since ancient times, extracted from weld, young fustic, dyer's broom, sawwort and the berries of some species of Rhamnus. Later on, old fustic and quercitron bark were introduced as sources of yellow colours.The method is based on the solvent extraction of flavonoids from raw plant materials (weld, dyer's broom and old fustic), aged and not aged alum-mordanted wool dyed specimens; subsequently, flavonoids are derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide and analysed by GC-MS. The method easily allows the identification of a dyestuff by the detection of the molecular markers apigenin, luteolin, genistein, morin, maclurin, together with 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4,6- trihydroxybenzoic acid, which survive in aged textiles. Two photo-oxidative degradation pathways for colour fading, one involving the mordant metallic ion and the other the light as a catalyst, are suggested.
2007
- Vibrational study of tamoxifen citrate polymorphism
[Articolo su rivista]
Gamberini, Maria Cristina; Baraldi, Cecilia; A., Tinti; Palazzoli, Federica; Ferioli, Valeria
abstract
The trans isomer of (Z)-2-[p-(1,2-diphenyl-butenyl)phenoxy]-N,N-dimethyletylamine (tamoxifen) is well known for its endocrine activity as an antiestrogenic agent. Its citrate salt, a widely used pharmaceutical agent, appears in three main polymorphic forms, two of which are well known (I and II) and another form not yet well evidenced.A vibrational study has been conducted for identifying the two known polymorphic forms of tamoxifen citrate (I and II) and for characterising the other form (form III) examined in this study.Other techniques for the characterization of the different polymorphs, such as XRDP, have been used
2006
- Analisi del contenuto di alcuni Unguentari Pompeiani
[Articolo su rivista]
Baraldi, Pietro; C., Fagnano; Baraldi, Cecilia; Gamberini, Maria Cristina
abstract
Una ricerca svolta sul contenuto di un gruppo di balsamari di Pompei ha portato ad evidenziare una serie di composti organici di varia natura. Mediante tecniche di spettroscopia infrarossa, microRaman e di gascromatografia applicata alla spettrometria di massa si sono identificati vari componenti noti e alcuni finora incogniti. I composti inorganici identificati possono fornire indicazioni sulla provenienza di materiali o preferenze locali per prodotti disponibili, le sostanze organiche, le tecnologie di preparazione del cosmetico. In generale, dall'esame dei dati qui riportati, risulta una cosmesi di tipo economico, rispetto a siti contemporanei posti in zone limitrofe. Non mancano però alcune singolarità, come l'impiego dell' huntite e della jarosite, materiali di probabile provenienza egiziana.
2006
- Gli unguentari pompeiani e il loro contenuto -prima parte
[Articolo su rivista]
Baraldi, Cecilia; Gamberini, Maria Cristina; Baraldi, Pietro; Mp, Colombini; E., Ribechini
abstract
Il gruppo di studio sulla cosmesi antica e moderna, costituito da ricercatori delle Università di Modena e Reggio Emilia e di Pisa, ha analizzato il contenuto di un gruppo di balsamari di area Campana. Mediante tecniche di spettroscopia infrarossa, microscopia Raman e di gascromatografia abbinata alla spettrometria di massa è stato possibile identificare componenti di varia natura tra i quali alcuni finora sconosciuti in questo campo. Una serie di composti inorganicipresenti fanno pensare alle preferenze delle matrone romane, altri alle vie commerciali diapprovvigionamento, altri ancora alle tecnologie per l’elaborazione del cosmetico. In generale, è possibile rilevare l’impiego di materiali di varia origine, di larga diffusione e di talora complessa preparazione. Non mancano però alcune singolarità,che si riferiscono all’uso di prodotti e tonalità particolari, di probabile provenienza extraitalica.
2006
- Gli unguentari pompeiani e il loro contenuto -seconda parte
[Articolo su rivista]
Baraldi, Cecilia; Gamberini, Maria Cristina; Baraldi, Pietro; Mp, Colombini; E., Ribechini
abstract
Il gruppo di studio sulla cosmesi antica e moderna, costituito da ricercatori delle Università di Modena e Reggio Emilia e di Pisa, ha analizzato il contenuto di un gruppo di balsamari di area Campana. Mediante tecniche di spettroscopia infrarossa, microscopia Raman e di gascromatografia abbinata alla spettrometria di massa è stato possibile identificare componenti di varia natura tra i quali alcuni finora sconosciuti in questo campo. Una serie di composti inorganici presenti fanno pensare alle preferenze delle matrone romane, altri alle vie commerciali di approvvigionamento, altri ancora alle tecnologie per l’elaborazione del cosmetico. In generale, è possibile rilevare l’impiego di materiali di varia origine, di larga diffusione e di talora complessa preparazione. Non mancano però alcune singolarità, che si riferiscono all’uso di prodotti e tonalità particolari, di probabile provenienza extraitalica.
2006
- Investigation on a Roman copper alloy artefact from Pompeii (Italy)
[Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; Ferrari, Giorgia; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo
abstract
A selection of samples, obtained from a particular copper-alloy domestic artefact of Roman style from Pompeii, has been analysed by using different techniques (IR, Raman, SEM-EDX, FAAS), in order to investigate the chemical nature and composition of the metals utilised for such manufacturing pieces. The surface analysis of the bright red metallic microfragments conducted by different analytical techniques, emphasises the presence of pure unalloyed copper and confirms the absence of other metallic species on the upper layers. On the contrary, the mapping analysis of the section of the laminar metal of the investigated sample shows a consistent enrichment in tin content. Finally, destructive analysis by FAAS confirms that the artefact looks like a bronze metal alloy, with a medium Sn content of about 6.5%
2006
- Solid state characterization of chloramphenicol palmitate. Raman spectroscopy applied to pharmaceutical polymorphs
[Articolo su rivista]
Gamberini, Maria Cristina; Baraldi, Cecilia; A., Tinti; Rustichelli, Cecilia; Ferioli, Valeria; Gamberini, Gianfranco
abstract
A pharmaceutical active compound, chloramphenicol palmitate, appears in three polymorphic forms, that can be observed at room temperature.The stable form A (biologically inactive modification), the meta-stable form B (active modification) and unstable form C were found to have distinct Raman spectra, with bands attributable to the different polymorphs.The use of hot-stage Raman microscopy (the direct coupling of Raman microscopy and hot-stage) is demonstrated for the drug substance chloramphenicol palmitate form C. All modifications of form C were produced and identified by hot-stage Raman microscopy. A close correlation of thermal and spectroscopic information was achieved by this combination of techniques.As reported in several pharmacopoeias, the content of form A should be less than 10%; therefore, a mixture of 10% (w/w) A in B was prepared, and the presence of the characteristic bands of form A after subtraction of the pure B was revealed. Moreover, mixtures between 2 and 12% (w/w) A in B were investigated and the intensity ratio (as peak area) I413–435/I1035–1158 as a function of A percentage has been demonstrated to show a linear trend. Other methods for the characterization of polymorphs were used: Fourier transform infrared spectroscopy (FT-IR), Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), Differential scanning calorimetry (DSC) and X-ray powder diffraction (XRPD).
2005
- Diagnostics on Scagliola Altar Frontals from the Area of Modena (Italy)
[Abstract in Atti di Convegno]
Baraldi, Pietro; M. P., Colombini; Baraldi, Cecilia
abstract
Traditionally, the town of Carpi is considered the home of scagliola. The old attestations of scagliola masters starting from the 16th century and the presence on the spot of hundreds of altar frontals and other lithurgical and domestic objects testify this tradition, besides the presence of a Municipal Museum of Scagliola in the Castle of Pio family. The art of scagliola developed from the simple white-and-black artifacts to the polychrome altar frontals and tables whit elaborate workmanship, and spread beyond the Modena area, as it is testified by both the works in adjacet provinces and regions, and the propagation of schools whit the transfer of masters outside the Emilia region. Recent studies carryed out by means of non destructive techniques have put in evidence the correspondences among the techniques identified for the preparation of the artifacts and the literature sources. Some more manuscripts preserved in the Archivio Storico of Carpi and amounting to the age of the ruling by the Pio family, indicate a series of materials for preparing the support and the coloured dough. We report the results of a research carried out by means of different analytical methods for the identification of the materials employed in the execution of these artefacts. The research was carried out in order to identify some more correspondences between measurements and old sources and to ascertain possible differences among ateliers or schools. Whereas Raman microscopy enabled to find out the pigments and dyes used for the scagliola, Gas-Chromatografy coupled whit Mass Spectrometry gave micro-distructively information on the nature of binders and of the products for the surface finish. The application of these techniques to the study of some altar frontal samples from the area of Carpi, Modena and Reggio has led to the identification of pigments such as minium, vermillon, lazurite, orpiment, red and yellow ochres, lead white and lampblack, and of dyes such as indigo, saffron, and of a red dye with a clear spectrum, but unknown nature. The binder corresponds to an animal glue that is locally known as “colla garavella” or “german glue”, the preparation of which is reported in many medieval and Renaissance recipe-books.
2005
- Direct HPLC enantioseparation of Cetirizine Hydrochloride on polysaccharide-based chiral stationary phases
[Abstract in Atti di Convegno]
Rustichelli, Cecilia; Gamberini, Maria Cristina; Baraldi, Cecilia; Ferioli, Valeria; Gamberini, Gianfranco
abstract
Cetirizine hydrochloride is a non-sedating H1-receptor antagonist used in patients whit urticaria and allergic rhinitis. It is frequently administrated as racemate; although recent data demonstrate that the antihistaminergic activity of the racemate is primarily due to the levo-enantiomer, while dextrocetirizine failed to demonstrate any significant activity. Moreover levocetirizine exhibits a more pharmacokinetic behaviour due to a lower volume of distribution and a slower renal clearance; therefore cetirizine has been recently marked as levo- enantiomer (Xyzal) in Europe. In order to study the simultaneous determination of (+)- and (-)- cetirizine hydrochloride we have developed direct separation methods by HPLC on polysaccharide-based chiral stationary phases. Satisfactory results were achieved on a Chiralcel OD-R column under gradient elution whit a mobile phase of acetonitrile and perchlorate buffer (0.3M; pH 3.30); these conditions allowed the complete enantioseparations (Rs= 1.65) of the analyte in times suitable for routine analyses. Complete separations in short analysis time (Rs= 1.61) were performed on a Chiralcel OD column under isocratic normal phases conditions (85% n-hexane and 15% ethanol, containing 0.15% trifluoroacetic acid). These conditions were applied to the determination of the stability of cetirizine hydrochloride in methanolic solutions and our studies revealed the formation of an achiral and a chiral degradation product. The developed procedures could be of interest for routine analyses and stereoselective investigations.
2005
- Raman Spectroscopy applied to polymorphism of Tamoxifene Citrate
[Abstract in Atti di Convegno]
Gamberini, Maria Cristina; Rustichelli, Cecilia; Baraldi, Cecilia; Ferioli, Valeria; Gamberini, Gianfranco
abstract
Different strategies for a systematic study of polymorphism can be applied: XRPD, DSC, FT-IR and Raman spectroscopy. Unlike X-ray diffraction Raman microscopy, a non-destructive and non-invasive technique, can be applied to pure solids or dosage forms without any sample preparation. The ability of Raman spectroscopy to discriminate between polymorphs has been demonstrated: different crystal structures usually show intensity and frequenciey changes in the Raman spectrum particularly in the rather crowded area from ~ 500 to ~ 1700 cm-1, known as “fingerprint region” which contains the majority of the bands used to identify a particular material. The use of Raman microscopy has been demonstrated for Tamoxifen Citrate: its trans isomer is in fact well known for its endocrine activity as an antiestrogenic agent. Tamoxifen citrate exists in two polymorphic form A and B, Which were found to have a distinct micro Raman spectrum whith bands attributable to the different forms. Another possible form was found and its Raman spectrum is different from the others. Other methods for the characterization of the three forms were used: XRDP, DSC, ATR/FTIR. Because of its non-invasive character, by focusing the micro Raman laser in to a capillary tube the convertion at room temperature of a suspension in ethanol of form A to B has been observed. Finally, the sensitivity to polymorphism of Raman spectroscopy, which makes it an ideal candidate for studies of crystal forms of Pharmaceutical compounds, could be analysed.
2005
- Studi sulla Cosmesi in Area Vesuviana
[Relazione in Atti di Convegno]
Baraldi, Cecilia
abstract
Sono stati analizzati campioni provenienti da un gruppo di balsamari di area Campana. Mediante tecniche di spettroscopia infrarossa, microscopia Raman e di gascromatografia abbinata alla spettrometria di massa è stato possibile identificare componenti di varia natura tra i quali alcuni finora sconosciuti in questo campo. Una serie di composti inorganici presenti fanno pensare alle preferenze delle matrone romane, altri alle vie commerciali di approvvigionamento, altri ancora alle tecnologie per l’elaborazione del cosmetico. In generale, è possibile rilevare l’impiego di materiali di varia origine, di larga diffusione e di talora complessa preparazione. Non mancano però alcune singolarità, che si riferiscono all’uso di ingredienti inusuali e tonalità particolari, di probabile provenienza extraitalica.
2004
- Contenuto dei balsamari vitrei
[Capitolo/Saggio]
Baraldi, Cecilia
abstract
Il contributo riporta un consuntivo delle analisi effettuate sui reperti vitrei a valenza cosmetica esposti nella mostra Vitrum, Firenze, Palazzo Pitti, dal 27 Marzo al 31 Ottobre 2004. Le anlisi condotte su cosmetici romani di provenienza pompeiana sono state condotte mediante differenti tecniche. La componente inorganica è stata valutata mediante spettroscopia infrarossa e microscopia Raman; mentre le tracce delle componenti organiche sono state analizzate mediante gascromatografia abbinata alla spettrometria di massa. Interessanti il rinvenimento di: carbone, talora di orgine vegetale e talora animale; cerussite ; "bianco di conchiglia"; goethite. Per la componente organica: patchoulolo e patchoulene, omphacium e terpeni riscontrabili nelle essenze di diverse specie vegetali.
2004
- Ricerca sul contenuto dei Balsamari di Oplontis
[Articolo su rivista]
Baraldi, Pietro; Baraldi, Cecilia; C., Fagnano; Ferioli, Valeria; Gamberini, Maria Cristina
abstract
Sono stati presi in considerazione i balsamari rinvenuti al momento dello scavo della villa B di Oplontis. Mediante moderne tecniche di analisicome la gascromatografia abbinata alla spettrometria di massa e la spettroscopia infrarossa sono stati identificati sia i componenti inorganici che organici. Il contenuto dei balsamari è risultato prevalentemente di origine organica e permette di ipotizzare dai residui individuati la presenza originaria di grassi e di essenze di provenienza anche extraeuropea. Questo permette da una parte di comprovare una abilità locale per l'estrazione per l'estrazione e la lavorazione di prodotti cosmetici e dall'altra l'esistenza di vie commerciali dall'Estremo Oriente nel I sec. d.C. Alcune delle presenze accertate sono indicative dell'elevato livello di vita degli abitanti della domus.
2002
- Antico ricettario modenese di mano femminile per miniare e dorare. Note sulle specie vegetali e sui composti chimici menzionati
[Articolo su rivista]
Baraldi, Pietro; Baroni, Roberta; Baraldi, Cecilia; Sgarbi, Elisabetta
abstract
L'antico manoscritto, qui trascritto e commentato, consiste in una raccolta di Ricette per miniare, per applicare l'oro, per stemperare il cinabro, per ottenere l'acqua verde e il colore azzurro, per brunire ecc... e fa parte del vasto lascito del conte modenense G. Campori destinato alla Biblioteca Estense Universitaria. Nel breve manuale sono riportati composti diversi, minerali, succhi estratti da piante, terre di origine non italiana, utilizzati in tecniche particolari di pittura, scrittura con l'oro e soprattutto di brunitura.
2002
- Caratterizzazione dei contenuti cosmetici nei balsamari di Oplontis
[Abstract in Atti di Convegno]
Baraldi, Pietro; Ferioli, Valeria; Benedetti, Adriano; Baraldi, Cecilia; Zannini, Paolo
abstract
Lo scavo, condotto secondo metodologie scientifiche avanzate, del sito di Oplontis rappresenta per l’archeologo e l’archeometra una possibilità nuova di indagine e comprensione di una somma di situazioni importanti. Una di queste è rappresentata certamente dal rinvenimento di 17 balsamari pressoché intatti contenenti una quantità considerevole di residuo. La collaborazione con la Soprintendenza Archeologica di Pompei ci ha consentito di accedere ai reperti e di eseguire per la prima volta prelievi di campioni da sottoporre all’analisi.I campioni si presentavano più o meno scuri, ma non contenevano pigmenti neri, bianchi o di altro colore chiaramente osservabili. Alcuni presentano un odore caratteristico, simile a quello della colofonia. Per i campioni è stata seguita una doppia strada di indagine: la spettroscopia FT-IR e la gascromatografia GC-MS su estratti ottenuti con le metodiche internazionali. Le analisi in GC-MS hanno mostrato che gli estratti metanolici presentano una serie di componenti che vanno dal patchoulolo ad acidi grassi liberi, ad esteri, ad idrocarburi e a terpeni classici. L’esame degli spettri IR ha evidenziato la presenza di acidi grassi liberi ed esteri e tracce di cere.La presenza del patchoulolo risulta di particolare interesse in quanto si tratta di un componente presente nell’estratto del Pogostemon cablin, una pianta originaria dell’India e dell’estremo Oriente, utilizzata anche in epoca recente per la produzione di profumi. La sua provenienza dall’area indiana consente di ipotizzare l’elevato pregio del cosmetico, che ne consentiva l’utilizzo alle classi sociali elevate quali quelle del contesto di Oplontis.
2002
- Mappatura e indagine sui reperti cosmetici rinvenuti a Pompei
[Abstract in Atti di Convegno]
Ferioli, Valeria; Baraldi, Pietro; C., Fagnano; Gamberini, Maria Cristina; Baraldi, Cecilia
abstract
La città di Pompei rappresenta un unicum per qualità e quantità di reperti archeologici anche di tipo cosmetico. Da un’indagine condotta in archivio in collaborazione con il Laboratorio della Soprintendenza Archeologica di Pompei è emersa la presenza di un numero elevato di unguentari, balsamari e alabastra. Purtroppo le pratiche di reperimento e conservazione dei tempi passati ha eliminato il contenuto di gran parte dei contenitori considerati. In poco più di un centinaio di essi rispetto ad un totale di oltre un migliaio sono state rinvenute quantità più o meno cospicue del contenuto. Di questi è stato considerato un gruppo che presentava materiale polverulento colorato.
A differenza dei balsamari di Oplontis, quelli di Pompei sono apparsi tutti di natura molto differente. Un gran numero conteneva polvere di un colore o nero vellutato o bianco candido e solo in alcuni casi si è rilevato un colore differente. Per l’identificazione della natura dei cosmetici sono state impiegate la spettroscopia FT-IR associata alla microscopia Raman e la gascromatografia abbinata alla spettrometria di massa GC-MS.
Gli spettri infrarossi e Raman hanno consentito di accertare che i prodotti neri sono costituiti da carbone di probabile origine vegetale, un tipo di kohl facilmente reperibile, quelli bianchi da gesso diidrato, talora mescolato con calcite, il giallo da goethite. Non sono mancate identificazioni insolite, come ad es. cerussite, aragonite, anglesite, sulla cui origine sono possibili varie ipotesi.
L’analisi degli estratti metanolici mediante GC-MS in molti casi non ha mostrato la presenza di componenti organici. Questo può indicare che venivano impiegati prevalentemente prodotti inorganici, ma anche che nei balsamari i cosmetici erano conservati allo stato di polvere e che solo al momento dell’uso una piccola quantità veniva mescolata con un legante che ne consentisse l’applicazione. La natura del contenuto dei balsamari fa propendere per un campionario di prodotti ristretto e di tipo popolare, rispetto a quelli corrispondenti di Oplontis.
L’analisi della distribuzione statistica dei balsamari, anche non aventi contenuto, è risultato di interesse in quanto può, in qualche rispetto, essere collegato all’evento finale della città nel 79 d.C. e al valore e al significato attribuito ai balsamari in epoca Romana.
La ricerca è stata condotta sul finanziamento CNRC00BEAC_002
Si ringrazia la Soprintendenza Archeologica di Pompei per aver reso possibile la Ricerca.