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Andrea MARCHETTI
Professore Associato
Dipartimento di Scienze Chimiche e Geologiche - Sede Dipartimento di Scienze Chimiche e Geologiche
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Pubblicazioni
2024
- Electrochemical growth of PAH-dendrimers supramolecular films. An integrated experimental-theoretical approach
[Articolo su rivista]
Bonechi, M.; Marchetti, A.; Giurlani, W.; Vanossi, D.; Pasquali, L.; Campidelli, S.; Fontanesi, C.; Innocenti, M.
abstract
The electrochemical oxidation of a polyphenylene-based dendrimer containing 96 sp2 carbon atoms (PPD) allows
obtaining a more extended conjugated carbon framework, polymer PPD (pPPD), starting from the parent fused-
benzene-based PPD. The structure and electronic properties of the polymeric thin film obtained by electrochemical
oxidation have been characterized by Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy.
Structural properties of the thin film formed upon electrochemical oxidation of PPD, are characterized
by Matrix-Assisted Laser Desorption/Ionization (MALDI-TOF) and Gel-Permeation Chromatography (GPC)
measurements. The degree of order of the layers as well as the virtual, and occupied, electronic states are
addressed and exploited to obtain information on conjugation and oligomer size within the polymeric pPPD film.
The experimental results are compared with DFT, B3LYP/6–31G(d), calculations. The overall results suggest that
the thin film formed on the electrode surface is mainly formed by PPD dimer and trimer upon electrochemical
oxidation.
2023
- Characterization of Some Stilbenoids Extracted from Two Cultivars of Lambrusco-Vitis vinifera Species: An Opportunity to Valorize Pruning Canes for a More Sustainable Viticulture
[Articolo su rivista]
D'Eusanio, Veronica; Genua, Francesco; Marchetti, Andrea; Morelli, Lorenzo; Tassi, Lorenzo
abstract
Pruning canes from grape vines are valuable byproducts that contain resveratrol and other health-boosting stilbenoids. This study aimed to assess the effect of roasting temperature on the stilbenoid content of vine canes by comparing two Vitis vinifera cultivars, Lambrusco Ancellotta and Salamino. Samples were collected during different phases of the vine plant cycle. One set was collected in September after the grape harvest and was air-dried and analyzed. A second set was obtained during vine pruning in February and evaluated immediately after collection. The main stilbenoid identified in each sample was resveratrol (similar to 100-2500 mg/kg), with significant levels of viniferin (similar to 100-600 mg/kg) and piceatannol (similar to 0-400 mg/kg). Their contents decreased with increasing roasting temperature and residence time on the plant. This study provides valuable insights into the use of vine canes in a novel and efficient manner, which could potentially benefit different industries. One potential use involves the roasted cane chips to accelerate the aging of vinegars and alcoholic beverages. This method is more efficient and cost-effective than traditional aging, which is slow and unfavorable from an industrial perspective. Furthermore, incorporating vine canes into maturation processes reduces viticulture waste and enhances the final products with health-promoting molecules, such as resveratrol.
2023
- Exploring the Mineral Composition of Grapevine Canes for Wood Chip Applications in Alcoholic Beverage Production to Enhance Viticulture Sustainability
[Articolo su rivista]
D'Eusanio, Veronica; Genua, Francesco; Marchetti, Andrea; Morelli, Lorenzo; Tassi, Lorenzo
abstract
2023
- Optimization of an analytical method based on SPME-Arrow and chemometrics for the characterization of the aroma profile of commercial bread
[Articolo su rivista]
Pellacani, Samuele; Durante, Caterina; Celli, Silvia; Mariani, Manuel; Marchetti, Andrea; Cocchi, Marina; Strani, Lorenzo
abstract
A SPME-Arrow GC-MS approach, coupled with chemometrics, was used to thoroughly investigate the impact of different types of yeast (sourdough, bear's yeast and a mixture of both) and their respective leaving time (one, three and five hours) on VOCs of commercial bread samples. This aspect is of paramount importance for the baking industry to adjust recipe modifications and production parameters, as well as to meet consumer needs in formulating new products.
A deep learning approach, PARADISe (PARAFAC2-based deconvolution and identification system), was used to analyse the obtained chromatograms in an untargeted manner. In particular, PARADISe, was able to perform a fast deconvolution of the chromatographic peaks directly from raw chromatographic data to allow a putatively identification of 66 volatile organic compounds, including alcohols, esters, carboxylic acids, ketones, aldehydes. Finally, Principal Component Analysis, applied on the areas of the resolved compounds, showed that bread samples differentiate according to their recipe and highlighted the most relevant volatile compounds responsible for the observed differences.
2023
- Rosaceae Nut-Shells as Sustainable Aggregate for Potential Use in Non-Structural Lightweight Concrete
[Articolo su rivista]
D’Eusanio, Veronica; Bertacchini, Lucia; Marchetti, Andrea; Mariani, Mattia; Pastorelli, Stefano; Silvestri, Michele; Tassi, Lorenzo
abstract
2023
- Volatile Aroma Compounds of Gavina® Watermelon (Citrullus Lanatus L.) Dietary Fibers to Increase Food Sustainability
[Articolo su rivista]
D'Eusanio, Veronica; Maletti, Laura; Marchetti, Andrea; Roncaglia, Fabrizio; Tassi, Lorenzo
abstract
2023
- Waste By-Product of Grape Seed Oil Production: Chemical Characterization for Use as a Food and Feed Supplement
[Articolo su rivista]
D'Eusanio, Veronica; Malferrari, Daniele; Marchetti, Andrea; Roncaglia, Fabrizio; Tassi, Lorenzo
abstract
2022
- Application of experimental design in HPLC method optimisation for the simultaneous determination of multiple bioactive cannabinoids
[Articolo su rivista]
Durante, C.; Anceschi, L.; Brighenti, V.; Caroli, C.; Afezolli, C.; Marchetti, A.; Cocchi, M.; Salamone, S.; Pollastro, F.; Pellati, F.
abstract
The scientific interest in Cannabis sativa L. analysis has been rapidly increasing in recent years, especially for what concerns cannabinoids, plant secondary metabolites which are well known for having many biological properties. High-performance liquid chromatography (HPLC) is frequently used for both the qualitative and quantitative analysis of cannabinoids in plant extracts from C. sativa and its derived products. Many studies have been focused on the main cannabinoids, such as Delta(9)-tetrahydrocannabinolic acid (Delta(9)-THCA), cannabidiolic acid (CBDA), cannabigerolic acid (CBGA) and their decarboxylated derivatives, such as Delta(9)-tetrahydrocannabinol (Delta(THC)-T-9), cannabidiol (CBD) and cannabigerol (CBG). In addition to the abovementioned compounds, the plant produces other metabolites of the same chemical class, and some of them have shown interesting biological activities.In the light of this, it is important to have efficient analytical methods for the simultaneous separation of cannabinoids, which is quite complex since they present similar chemical-physical characteristics. The present work is focused on the use of the Design of Experiments technique (DoE) to develop and optimise an HPLC method for the simultaneous separation of 14 cannabinoids. Experimental design optimisation was applied by using a Central Composite Face-Centered design to achieve the best resolution with minimum experimental trials. Five significant variables affecting the chromatographic separation, including ammonium formate concentration, gradient elution, run time and flow rate, were studied. A multivariate strategy, based on Principal Component Analysis (PCA) and Partial Least Squared (PLS) regression, was used to define the best operative conditions. The developed method allowed for the separation of 12 out of 14 cannabinoids. Due to co-elution phenomena, HPLC coupled with a triple quadrupole mass analyser (HPLC-ESI-MS/MS) was applied, monitoring the specific transitions of each compound in the multiple reaction monitoring (MRM) mode. Finally, the optimised method was applied to C. sativa extracts having a different cannabinoid profile to demonstrate its efficiency to real samples.The methodology applied in this study can be useful for the separation of other cannabinoid mixtures, by means of appropriate optimisation of the experimental conditions.
2022
- Candying process for enhancing pre-waste watermelon rinds to increase food sustainability
[Articolo su rivista]
Maletti, Laura; D'Eusanio, Veronica; Lancellotti, Lisa; Marchetti, Andrea; Pincelli, Luca; Strani, Lorenzo; Tassi, Lorenzo
abstract
This work describes two alternative laboratory methods ’candying fruit’ methods of fresh mesocarp of Crimson
sweet watermelon, a typical waste and unappetizing material. Our experimental candying process was conducted
by slow osmosis, lasting 24 weeks at room temperature. It was activated with granular sucrose according to our
two alternative laboratory methods, WET and DRY. Fresh watermelon rinds were transformed into candied fruit
with excellent flavor and aromas. The aromatic profile of all the materials was characterized with HS-SPME-GC–
MS technique. The results highlighted some significant differences in the Volatile Organic Compounds fraction,
probably attributable both to the cultivar and to the two candying methods, as verified also by a panel test. The
class of alcohols remains almost constant in all the samples. Terpenoids are highly present in FRESH samples,
while they disappear in DRY candied ones. Acetate esters are absent in FRESH rinds, they reach the maximum
level in WET, and stop at the middle in DRY samples. The trend of the values relating to the class of acids is
opposite: absent in the FRESH aromatic profile, maximum and average for DRY and WET samples, respectively.
2022
- Comparative Analysis of VOCs from Winter Melon Pomace Fibers before and after Bleaching Treatment with H2O2
[Articolo su rivista]
Maletti, Laura; D'Eusanio, Veronica; Durante, Caterina; Marchetti, Andrea; Pincelli, Luca; Tassi, Lorenzo
abstract
In this study, the trend of Volatile Organic Compounds (VOCs) in dietary fiber samples from the winter melon (Cucumis Melo var. Inodorus, Yellow Canary type) were investigated. This foodstuff, obtained as a by-product of agri-food production, has gained increasing attention and is characterized by many bioactive components and a high dietary-fiber content. As regards fiber, it is poorly colored, but it may be whitened by applying a bleaching treatment with H2O2. The result is a fibrous material for specific applications in food manufacturing, for example, as a corrector for some functional and technological properties. This treatment is healthy and safe for consumers and widely applied in industrial food processes. In this study, a method based on headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC-MS) was applied for the characterization of the aromatic profile of the dried raw materials. Furthermore, VOC variation was investigated as function of the bleaching treatment with H2O2. The bleached samples were also analyzed after a long storage period (24 months), to assess their stability over time. As a result, the VOC fraction of the fresh raw fiber showed nine classes of analytes; these were restricted to seven for the bleached fiber at t0 time, and further reduced to four classes at the age of 24 months. Alcohols were the main group detected in the fresh raw sample (33.8 % of the total chromatogram area), with 2,3-butanediol isomers as the main compounds. These analytes decreased with time. An opposite trend was observed for the acids (9.7% at t0), which increased with time and became the most important class in the 24-month aged and bleached sample (57.3%).
2022
- Molecular electrochemistry. An overview of a cross-field: Electrochemistry/spectroscopic/theoretical integrated approach
[Articolo su rivista]
Salzillo, T.; Marchetti, A.; Vejpravova, J.; Fanjul Bolado, P.; Fontanesi, C.
abstract
This work summarizes state-of-the-art results achieved by combining, in a synergetic approach, the outcome obtained by electrochemical, spectroscopic and theoretical methods. A number of selected case-studies are reported, where such a synergetic approach enables to draw a complete picture of complex experimental systems. Finally, the relevance of the combined experimental and theoretical approach in solid-state electrochemistry, a territory amidst novel concepts in solid-state electronics, is recapped.
2022
- Resorcinol electropolymerization process obtained via electrochemical oxidation
[Articolo su rivista]
Bonechi, M.; Giurlani, W.; Stefani, A.; Marchetti, A.; Innocenti, M.; Fontanesi, C.
abstract
The electrochemical oxidation of resorcinol is experimentally studied on platinum, palladium and glassy carbon (GC) electrodes. The results of an exhaustive electrochemical characterization are presented, and integrated with the outcome of complementary chromatographic analytical techniques: LC-DAD and LC-MS. We demonstrate that upon electrochemical oxidation resorcinol polymerizes following an efficient and facile process, and once the electropolymerization is triggered a polymer film can be easily grown. The latter film features also good adhesion on the electrode surface.
2022
- VOCs Analysis of Three Different Cultivars of Watermelon (Citrullus lanatus L.) Whole Dietary Fiber
[Articolo su rivista]
Maletti, Laura; D'Eusanio, Veronica; Durante, Caterina; Marchetti, Andrea; Tassi, Lorenzo
abstract
In this study, the trend of VOCs of dietary fiber samples, coming from three different watermelon cultivars Citrullus lanatus L. (variety Gavina®®, Crimson sweet, and Asahi myiako) was investigated. This foodstuff, obtained as a by-product of residual agri-food production, has gained increasing attention because of its many bioactive components and high dietary fiber content. The result is a fibrous material for specific applications in food manufacturing, such as corrector for some functional and technological properties. In this study, a method based on headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC–MS) was used to characterize the aromatic profiles of the dried raw materials. Therefore, the VOCs of the samples of the three cultivars were investigated. Experimental results have shown that watermelon fibers generate VOCs, which can be grouped into six common classes of analytes. The different distributions of the identified compounds made it possible to effectively differentiate the three cultivars studied based on their peculiar aroma profiles. In particular, Gavina®® fiber is distinguished by the high content of terpenes, Asahi myiako by the presence of aldehydes generated as fatty acid metabolites, and Crimson sweet by the higher content of acetyl esters.
2021
- 87Sr/86Sr ratio as traceability marker for Modena's balsamic vinegars
[Articolo su rivista]
Durante, C.; Lancellotti, L.; Manzini, D.; Rossi, M. C.; Sighinolfi, S.; Marchetti, A.; Tassi, L.
abstract
Geographical origin and authenticity of food are topics of interest for both consumers and producers. Among the different indicators used for traceability studies, n(87Sr)/n(86Sr) isotopic ratio has provided excellent results. In this study, the production chains of the balsamic vinegars of the Modena province, the Aceto Balsamico Tradizionale di Modena (ABTM) and the industrially made Aceto Balsamico di Modena (ABM) were investigated by using the n(87Sr)/n(86Sr) indicator. The geographical origin of the starting raw materials for the ABM production was investigated, as well as the variability of ABM samples of different production years, namely 2009, 2010, 2011 and 2014. The results show no significant variability among ABM samples of different production years and highlight the possibility to distinguish this product from the ABTM. Furthermore, the investigated indicator also confirms an objective link of the food with its starting raw material and the territory of origin of the grapes, assessing the discriminating power of n(87Sr)/n(86Sr) ratio for geographical traceability studies.
2021
- Analytical Concentrations of Some Elements in Seeds and Crude Extracts from Aesculus hippocastanum, by ICP-OES Technique
[Articolo su rivista]
Durante, C.; Cocchi, M.; Lancellotti, L.; Maletti, L.; Marchetti, A.; Sighinolfi, S.; Tassi, L.; Roncaglia, F.
abstract
The metal content in some samples of horse chestnut seeds (Aesculus hippocastanum) was monitored over time (years 2016, 2017, 2018, 2019) considering the two most common and representative Mediterranean varieties: the pure species (AHP, which gives white flowers) and a hybrid one (AHH, which gives pink flowers). The selected elemental composition of the samples was determined by applying the ICP-OES technique.
Several samples obtained from different preliminary treatments of the peeled seeds were examined, such as: i) floury samples (wild type) mineralized with the wet method; ii) the ashes of both AHP and AHH varieties; iii) the fraction of total inorganic soluble salts (TISS).
Furthermore, the hydroalcoholic crude extracts (as a tincture) were obtained according to the official Pharmacopoeia methods, and the relevant results were compared with those of a commercial sample, an herbal product - food supplement of similar characteristics. The main characteristics of this research work underline that the two botanical varieties give different distinctive characters, due to the Fe content (80.05 vs 1.42 mg / 100 g d.s., for AHP and AHH - wild type flour samples, respectively), along with K, Ca, Mn, Ni and Cu, which are more abundant in the AHP samples. Furthermore, the PCA analysis was applied to the experimental dataset in order to classify and discriminate the samples, in relation to their similar botanical origin, but different for the color of the bloom. These results can be useful for the traceability of raw materials potentially intended for the production of auxiliary systems of pharmacological interest.
2021
- On the Savéant's Concerted/Stepwise Model. The Electroreduction of Halogenated Naphthalene Derivatives as a Case Study
[Articolo su rivista]
Stefani, Andrea; Giurlani, Walter; Bonechi, Marco; Marchetti, Andrea; Preda, Giovanni; Pasini, Dario; Innocenti, Massimo; Fontanesi, Claudio
abstract
The electroreduction of 1-Br-2-naphthol is shown to be a not-additive process with respect to the results obtained with two structurally related chiral [1,1′-Binaphthalene]-2,2′-diol, 6,6′-dibromo and 1,1′-Binaphthalene,6,6′-dibromo-2,2′-dimethoxy compounds. The 1-Br-2-naphtol reduction is accompanied by the carbon bromine dissociation, eventually producing a film due to a fast radical-radical cross reaction. The film formation is not observed in the BINOL-like chiral halogen-derivatives.
2021
- Tracing geographical origin of Lambrusco PDO wines using isotope ratios of oxygen, boron, strontium, lead and their elemental concentration
[Articolo su rivista]
Lancellotti, L.; Sighinolfi, S.; Ulrici, A.; Maletti, L.; Durante, C.; Marchetti, A.; Tassi, L.
abstract
Wine identification is one of the most important aspects in the classification of wines and consumer protection. In particular, assuring wine authenticity is a crucial issue on which researchers are focusing on. This study aims to evaluate the feasibility of using chemical (B, Pb and Sr concentration) and isotopic compositions (δ11B, 20yPb/20xPb, 87Sr/86Sr and δ18O) of wine samples to trace their geographic origins. Different PDO Lambrusco wines coming from a confined area of northern Italy were analyzed and all the isotopic systematics were monitored by using a multi collector inductively coupled plasma mass spectrometer (MC-ICP/MS). The obtained results showed that boron isotope ratio measurements led to a satisfactory degree of accuracy and precision (measured value, n = 28, 11B/10B of NIST SRM 951a equal to 4.04343 ± 0.00178, (u = 2s) with a certified value of 4.04362 ± 0.00136 (u = 2s). Furthermore, in the present study, it has been possible to highlight significant differences among samples by means of one-way analysis of variance (ANOVA) and post hoc Tukey-Kramer test. Finally, Principal Component Analysis (PCA) was also carried out in order to evaluate to which extent the different PDOs can be distinguished from each other, taking into account the whole set of geographical origin descriptors. Although δ11B provided more sensitive information, the obtained results highlighted the important to consider the synergistic combination of all the investigated parameters to trace the different samples and the need to combine the obtained values with the same parameters evaluated in the soil, water and fertilizer as well.
2020
- Chemical Characterization Of Commercial Balsamic Vinegar Glaze
[Articolo su rivista]
Lancellotti, L.; Ulrici, A.; Sighinolfi, S.; Marchetti, A.
abstract
The present study reports the chemical characterization of commercial balsamic vinegar glaze (BVG), a side product of the world-famous Aceto Balsamico di Modena (ABM). BVG, originally a homemade sweet and sour sauce, is now produced on an industrial scale and is gaining a growing success. The determination of total titratable acidity, dry matter, ash, metals, sugars, phenolic acids and furfurals is reported for BVG samples of different batches and years of production. Principal component analysis (PCA) and ANOVA test were applied to evaluate the experimental data. The results showed that the chemical characteristics of the product are almost unchanged in the investigated years and well reflect the characteristics of the ABM. Moreover, it was found that potentially harmful species, namely furfural compounds and heavy metals, were at a lower concentration than that of homologous products. In particular, the concentration of heavy metals, such as Cu, Zn and Pb, suggests that a preventive demetallization of the BVG starting raw materials occurs.
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.
2020
- Use of lead isotopic ratios as geographical tracer for Lambrusco PDO wines
[Articolo su rivista]
Lancellotti, L.; Sighinolfi, S.; Marchetti, A.; Tassi, L.
abstract
In this study, the lead isotope signature was tested with the aim to verify its potential as geographic tracer for wine production and particularly for the Lambrusco PDO wines of the province of Modena (Italy). A solid phase extraction procedure, for separating lead from the investigated matrices, soil and wine, was optimized. Furthermore, different mathematical models, based on an exponential law and internal or external correction approach, were evaluated for the correction of instrumental mass dependent fractionation. The optimized analytical procedure yielded isotopic ratio data relative to the lead NIST 981 standard, 208Pb/206Pb = 2.16664 and 207Pb/206Pb = 0.914645, in good agreement both with the tabulated values and with the most recent literature data. Measured isotope ratio data highlight the contribute of multiple lead sources in bottled wine but different from the one present in soils.
2019
- INDURENTI NON MIGRATORI PER MATERIALI PROTEICI
[Brevetto]
Foca, Giorgia; Leoni, Diego; Lusvardi, Gigliola; Marchetti, Andrea; Roncaglia, Fabrizio; Tassi, Lorenzo
abstract
L’invenzione è relativa ad un processo di preparazione di nuovi materiali copolimerici a base di proteine di origine animale e di origine vegetale, indurite mediante agenti reticolanti a struttura furanica recanti gruppi funzionali carbonilici. Il processo produttivo dei biopolimeri consiste nella preparazione di una soluzione / sospensione delle proteine in ambiente acquoso per ottenere la massima distensione delle micelle, eventualmente miscelate con coloranti o pigmenti finemente dispersi, cui si aggiunge infine un agente cross-linkante di tipo furanico solubilizzato o sospeso in un solvente non acquoso e sotto vigorosa agitazione. I prodotti copolimerici termoindurenti ottenibili presentano caratteristiche meccaniche e prestazionali analoghe a quelle della galalite, e sono privi di qualunque rilascio di VOC.
2018
- Determination of glycerol carbon stable isotope ratio for the characterization of Italian balsamic vinegars
[Articolo su rivista]
Sighinolfi, Simona; Baneschi, Ilaria; Manzini, Simona; Tassi, Lorenzo; Dallai, Luigi; Marchetti, Andrea
abstract
The gas chromatographic-combustion-isotopic ratio mass spectrometry (GC-C-IRMS) approach was applied to
determine the compound-specific 13C/12C isotopic ratio of glycerol in balsamic vinegars of Modena (Italy). In
particular, Italian Protected Designation of Origin and Protected Geographical Indication balsamic vinegars,
namely the traditionally made Aceto Balsamico Tradizionale di Modena (ABTM) and the industrial Aceto
Balsamico di Modena (ABM) products, were analyzed and a first attempt at classification was carried out. The
carbon isotopic ratio of the glycerol polyalcohol varies on the basis of origin, varietal or provenance; therefore
the discriminating potentiality of this species might be useful to elucidate the balsamic vinegar production
process. To do this, a preliminary study was conducted and several marketable products, ABTM and ABM type,
were subjected to measurements in addition to samples coming from three ABTM cask series (batteria).
Experimental results highlighted the peculiarities of the two different production processes, suggesting the use of
the carbon isotopic ratio of glycerol as an additional tool for balsamic vinegar authentication.
2018
- Development of 87Sr/86Sr maps as targeted strategy to support wine quality
[Articolo su rivista]
Durante, Caterina; Bertacchini, Lucia; Cocchi, Marina; Manzini, Daniela; Marchetti, Andrea; Rossi, Maria Cecilia; Sighinolfi, Simona; Tassi, Lorenzo
abstract
This study summarizes the results obtained from a systematic and long-term project aimed at the development
of tools to assess the provenance of food in the oenological sector. In particular, 87Sr/86Sr isotope ratios were
measured on statistically representative set of soils, vine branches and wines sampled in the production district
of Modena, worldwide known for the Lambrusco wines production. The obtained data were used to build strontium
isotopic maps able to objectively support the Lambrusco PDO wines origin as well as other products of the
Modena district.
Finally, a strong relationship was found between the 87Sr/86Sr isotope ratios of soils and vine branches on a
large scale, highlighting and confirming once more the idea that plants can also represent an optimal sampling
device to support geographical traceability.
2018
- Influence of Chemical and Physical Variables on 87Sr/86Sr Isotope Ratios Determination for Geographical Traceability Studies in the Oenological Food Chain
[Articolo su rivista]
Sighinolfi, Simona; Durante, Caterina; Lancellotti, Lisa; Tassi, Lorenzo; Marchetti, Andrea
abstract
This study summarizes the results obtained from a systematic and long-term project aimed at the development of tools to assess the provenance of food in the oenological sector. 87Sr/86Sr isotope ratios were measured on a representative set of soils, branches, and wines sampled from the Chianti Classico wine production area. In particular, owing to the high spatial resolution of the 87Sr/86Sr ratio in the topsoil, the effect of two mill techniques for soil pretreatment was investigated to verify the influence of the particle dimension on the measured isotopic ratios. Samples with particle sizes ranging from 250 to less than 50 m were investigated, and the extraction was performed by means of the DIN 19730 procedure. For each sample, the Sr isotope ratio was determined as well. The obtained results showed that the 87Sr/86Sr ratio is not influenced by soil particle size and may represent an effective tool as a geographic provenance indicator for the investigated product.
2017
- Heavy isotopes
[Capitolo/Saggio]
Marchetti, Andrea; Durante, Caterina; Bertacchini, Lucia
abstract
Before to start writing this contribute on the use of “heavy elements isotope ratio” for food
traceability purposes, let us to underline our though about this nowadays important topic. In fact, it
is fairly common to closely link the use of isotope ratios parameters, either of light or bio elements
and heavy ones, as tools against food counterfeiting. Furthermore, it is worth to highlight how these
indicators tackled rather successfully this task. Nevertheless, another important aspect, largely
lacking (or neglected), needs to be considered. Indeed, geographical traceability of food should be
considered as an opportunity to increase food quality. The objective possibility to link the food to
its production territory (its “terroir”) represents an opportunity of growth for both the producers and
the consumers.
2016
- Dimensional changes in automotive Pouch Li-Ion Cells: A Combined Thermo-Mechanical/electrochemical study
[Articolo su rivista]
Gibellini, Erica; Lanciotti, Claudio; Giovanardi, Roberto; Bononi, Massimiliano; Davolio, Giovanni; Marchetti, Andrea; Fontanesi, Claudio
abstract
In this work it is proposed an integrated measurement system able to measure simultaneously mechanical properties, dimensional variations and Young modulus, of a pouch lithium-ion battery under operative conditions. At the same time, the designed integrated system allows also the measurement of both electrochemical main quantities (current and potentials) and temperature distribution. The complex testing capabilities system was implemented in an owner-lab-made apparatus. Experimental data collected both under normal operational conditions, as well as on abused batteries, allow to establish safer operational limits and to determine proper operation conditions to prevent the battery malfunctioning.
2016
- DoE optimizationofamercuryisotoperatiodeterminationmethodfor
environmentalstudies
[Articolo su rivista]
Berni, Alex; Baschieri, Carlo; Covelli, Stefano; Emili, Andrea; Marchetti, Andrea; Manzini, Daniela; Berto, Daniela; Rampazzo, Federico
abstract
By usingtheexperimentaldesign(DoE)technique,weoptimizedananalyticalmethodforthede-
termination ofmercuryisotoperatiosbymeansofcold-vapormulticollectorICP-MS(CV-MC-ICP-MS)to
provideabsoluteHgisotopicratiomeasurementswithasuitableinternalprecision.Byrunning32ex-
periments, theinfluence ofmercuryandthalliuminternalstandardconcentrations,totalmeasuringtime
and sample flow ratewasevaluated.MethodwasoptimizedvaryingHgconcentrationbetween2and
20 ngg1. Themodel finds outsomecorrelationswithintheparametersaffectthemeasurementspre-
cision andpredictssuitablesamplemeasurementprecisionsforHgconcentrationsfrom5ngg1 Hg
upwards.
The methodwassuccessfullyappliedtosamplesofManilaclams(Ruditapes philippinarum) coming
from theMaranoandGradolagoon(NEItaly),acoastalenvironmentaffectedbylongtermmercury
contamination mainlyduetominingactivity.Resultsshowdifferentextentsofbothmassdependent
fractionation (MDF)andmassindependentfractionation(MIF)phenomenainclamsaccordingtotheir
size andsamplingsitesinthelagoon.Themethodis fit fordeterminationsonrealsamples,allowingfor
the useofHgisotopicratiostostudymercurybiogeochemicalcyclesincomplexecosystems.
2016
- From soil to grape and wine: Variation of light and heavy elements
isotope ratios
[Articolo su rivista]
Durante, Caterina; Bertacchini, Lucia; Bontempo, Luana; Camin, Federica; Manzini, Daniela; Lambertini, Paolo; Marchetti, Andrea; Paolini, Mauro
abstract
In the development of a geographical traceability model, it is necessary to understand if the value of the
monitored indicators in a food is correlated to its origin or if it is also influenced by ‘external factors’ such
as those coming from its production. In this study, a deeper investigation of the trend of direct geographical
traceability indicators along the winemaking process of two traditional oenological products was
carried out. Different processes were monitored, sampling each step of their production (grape juice,
intermediate products and wine). The results related to the determinations of d18O, (D/H)I, (D/H)II,
d13C, d15N and 87Sr/86Sr have been reported. Furthermore, correspondence with the isotopic values coming
from the respective soil and vine-branch samples have been investigated as well, showing the optimal
traceability power of the monitored geographical tracers.
2015
- An analytical approach to Sr isotope ratio determination in Lambrusco wines for geographical traceability purposes
[Articolo su rivista]
Durante, Caterina; Baschieri, Carlo; Bertacchini, Lucia; Bertelli, Davide; Cocchi, Marina; Marchetti, Andrea; Manzini, Daniela; Papotti, Giulia; Sighinolfi, Simona
abstract
Geographical origin and authenticity of food are topics of interest for both consumers and producers.
Among the different indicators used for traceability studies, 87Sr/86Sr isotopic ratio has provided excellent
results. In this study, two analytical approaches for wine sample pre-treatment, microwave and low temperature
mineralisation, were investigated to develop accurate and precise analytical method for
87Sr/86Sr determination. The two procedures led to comparable results (paired t-test, with t < tcrit). Furthermore,
the precision of the whole analytical procedure was evaluated by using a control sample (wine
sample), processed during each sample batch (calculated Relative Standard Deviation, RSD%, equal to
0.002%. Lambrusco PDO (Protected Designation of Origin) wines coming from four different vintages
(2009, 2010, 2011 and 2012) were pre-treated according to the best procedure and their isotopic values
were compared with isotopic data coming from (i) soils of their territory of origin and (ii) wines obtained
by same grape varieties cultivated in different districts. The obtained results have shown no significant
variability among the different vintages of wines and a perfect agreement between the isotopic range
of the soils and wines has been observed. Nevertheless, the investigated indicator was not enough powerful
to discriminate between similar products. To this regard, it is worth to note that more soil samples
as well as wines coming from different districts will be considered to obtain more trustworthy results.
2015
- Application of strontium isotopic analysis to the promotion of the Vignola sweet cherry PGI
[Relazione in Atti di Convegno]
Berni, Alex; Baschieri, Carlo; Bertacchini, Lucia; Durante, Caterina; Marchetti, Andrea; Tassi, Lorenzo
abstract
The perceived quality of a food commodity may critically depend on the food origin, when regional traditions about the same food production are well-known [1]. This is certainly the case of Vignola Sweet Cherry, which is covered by the Protected Geographical Indication (PGI). The development of a territoriality model for Vignola Sweet Cherry PGI by means of analytical indicators hence represent a very intriguing task, useful for the promotion of the product itself.
In the framework of the pilot project “Ciliegia-UNIMORE2014”, we have assessed the effectiveness of the isotope ratio 87Sr/86Sr as direct traceability indicator, since this indicator have already provided excellent results in similar studies. [2].
Thanks to the collaboration of single producers and to the Association of sweet cherry, plum and typical fruit of Vignola, we have monitored the 87Sr/86Sr ratio in soils, branches and sweet cherry fruits of 3 producing fields, as well as in 100 fruit samples belonging to 20 different cultivars and coming from ten municipalities of the region of production. For a more complete characterization of the cherries, the concentration of 10 metals (major and trace constituents) and the polyphenols content have been determined.
2015
- Tracing mercury pathways in Augusta Bay (southern Italy) by total concentration and isotope determination
[Articolo su rivista]
Bonsignore, Maria; Tamburrino, Stella; Oliveri, Elvira; Marchetti, Andrea; Durante, Caterina; Berni, Alex; Quinci, Enzamaria; Sprovieri, Mario
abstract
The mercury (Hg) pollution of sediments is the main carrier of Hg for the biota and,
subsequently, for the local fish consumers in Augusta Bay area (SE Sicily, Italy), a coastal marine
system affected by relevant sewage from an important chlor-alkali factory. This relationship was
revealed by the determination of Mass Dependent (MDF) and Mass Independent Fractionation (MIF) of
Hg isotopes in sediment, fish and human hair samples. Sediments showed MDF but no MIF, while fish
showed MIF, possibly due to photochemical reduction in the water column and depending on the
feeding habitat of the species. Benthic and demersal fish exhibited MDF similar to that of sediments in
which anthropogenic Hg was deposited, while pelagic organisms evidenced higher MDF and MIF due to
photoreduction. Human hair showed high values of δ202Hg (offset of +2.2‰ with respect to the
consumed fish) and Δ199Hg, both associated to fish consumption.
2015
- Traditional balsamic vinegar and balsamic vinegar of Modena analyzed by nuclear magnetic resonance spectroscopy coupled with multivariate data analysis
[Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; Graziosi, Riccardo; Maietti, Annalisa; Tedeschi, Paola; Marchetti, Andrea; Plessi, Maria
abstract
Balsamic vinegar of Modena (BVM) and traditional balsamic vinegar of Modena (TBVM) are highly appreciated typical Italian products. The quality control and authentication assurance of both these balsamic vinegars are very important topics. In the recent years, the interest to develop new and standardized analytical procedures, able to further enhance the quality and commercial value of these typical and unique products and to preserve them from possible sophistications and adulterations, is increased. In this work, 76 samples of both BVM and TBVM were analized by 1H NMR spectroscopy coupled with multivariate data analysis. The spectral data were analyzed by principal component analysis (PCA), general discriminant analysis (GDA) and classification tree analysis (CTA). The best and very promising model was obtained by a GDA which shows 98.6% of total variance explained by the first canonical function and a predictive capacity of 98.4% with a good separation between clusters. The signals of 5-HMF, -glucopyranose, malic acid, succinic and acetic acids and a signal at 3.3 ppm referred to the glucose and fructose region were found to be the most statistically significant variables.
2014
- A mid level data fusion strategy for the Varietal Classification of Lambrusco PDO wines
[Articolo su rivista]
Silvestri, Michele; Elia, Andrea; Bertelli, Davide; Salvatore, Elisa; Durante, Caterina; Li Vigni, Mario; Marchetti, Andrea; Cocchi, Marina
abstract
Nowadays the necessity to reveal the hidden information from complex data sets is increasing due to the development of high-throughput instrumentation. The possibility to jointly analyze data sets arising from different sources (e.g. different analytical determinations/platforms) allows capturing the latent information that would not be extracted by the individual analysis of each block of data. Several approaches are proposed in the literature and are generally referred to as data fusion approaches. In this work a mid level data fusion is proposed for the characterization of three varieties (Salamino di Santa Croce, Grasparossa di Castelvetro, Sorbara) of Lambrusco wine, a typical PDO wine of the district of Modena (Italy). Wine samples of the three different varieties were analyzed by means of 1H-NMR spectroscopy, Emission-Excitation Fluorescence Spectroscopy and HPLC-DAD of the phenolic compounds.
Since the analytical outputs are characterized by different dimensionalities (matrix and tensor), several multivariate analyses were applied (PCA, PARAFAC, MCR-ALS) in order to extract and merge, in a hierarchical way, the information present in each data set.
The results showed that this approach was able to well characterize Lambrusco samples giving also the possibility to understand the correlation between the sources of information arising from the three analytical techniques.
2014
- AN ANALYTICAL APPROACH TO THE DEVELOPMENT OF GEOGRAPHICAL TRACEABILITY MODEL OF OENOLOGICAL PRODUCTS
[Poster]
Durante, Caterina; Bertacchini, Lucia; Cocchi, Marina; Manzini, Daniela; Rossi, Maria Cecilia; Camin, F.; Mattivi, F.; Marchetti, Andrea
abstract
Notwithstanding urbanization and globalization, the strengthening consumers interests towards food with a well-defined geographical origin has been kept constant and features such as food authenticity and traceability are becoming peculiar to the entire mankind. This work summarizes the preliminary results of a long term research project [AGER project] focused on the development of geographical traceability models of two typical Italian oenological products, Lambrusco PDO and TRENTODOC, by means of primary and secondary indicators. In particular, this work reviews the adopted strategy and the obtained results as regard the potentiality of primary geographical tracers, i.e. strontium isotopic ratio, 87Sr/86Sr and elemental content. The innovation of the adopted strategy lies in the use of a systematic approach for developing a geographical traceability model, which requires a deep knowledge of the whole matrices that characterised the investigated systems, namely soils, vine branches, grape juices, intermediate products and wines. For these reasons, a statistically representative sampling for Modena and Trento districts was performed and primary indicators were monitored in all the investigated matrices obtaining isotopic maps able to highlight the geographical link between the investigated wines and their territory of provenance.
2014
- Historical variations in the isotopic composition of mercury in sediment cores from northern Adriatic coastal environments
[Abstract in Atti di Convegno]
Covelli, Stefano; Baschieri, Carlo; Marchetti, Andrea; Acquavita, Alessandro; Berni, Alex; Spizzamiglio, Luca; Emili, Andrea
abstract
The results presented in this study involve the analysis of mercury (Hg) isotopes in two sediment cores from the Northern Adriatic. One core was collected in the Gulf of Trieste, an area contaminated by Hg residues produced by the Idrija Hg mine (Slovenia) during 500 years of activity and transported by the Isonzo River to the sea. The second core was collected in the Marano and Grado Lagoon, where Hg from a chlor-alkali plant was discharged into the Aussa-Corno River system flowing into this coastal environment. In this study, we used the high precision stable Hg isotope analysis of environmental samples made possible by continuous flow cold vapour introduction system coupled with MC-ICP-MS. The main aims of this research were to determine the isotope signatures of Hg from the two major sources of contamination, to compare them with the same signatures of the regional sedimentary background and to determine if Hg isotope compositions can be used to distinguish between different products deriving from exploitation and processing of Hg-bearing ore. Analysis of the dated core from the Gulf of Trieste showed that Hg concentration increased sharply at the beginning of 1800s, peaked before the first World War (23.32 µg g-1 in 1913) and then declined to a constant average of ≈ 8 µg g-1 in recent times (1980s-1990s). δ-values of the 199Hg/198Hg, 200Hg/198Hg, 201Hg/198Hg and 202Hg/198Hg ratios increased upward from the core bottom. Background sediments, where Hg concentration is 0.13 µg g-1, have an average δ202Hg of -3.93‰ ± 0.92‰ (n=5) which is significantly lower compared to recent contaminated sediments. The isotope signature of Hg deriving from mining activity was not altered by mass-independent fractionation (MIF) related to natural processes. Conversely, it showed mass-dependent fractionation (MDF), due to the transformation processes of Hg-bearing ores (mostly cinnabar but also native Hg in carboniferous schists) to by-products by the retorting processes which caused preferential depletion in the lighter isotopes. The isotope signatures of Hg were quite variable in the contaminated section of sediment cores where δ202Hg values ranged between -2.95‰ and 0.88‰. The variability in MDF is due to multiple sources, such as unroasted Hg ores and Hg waste calcines which, with different mixture and isotopic fingerprinting, affected the total isotopic composition of sediments.
2014
- MERCURY ISOTOPES DETERMINATIONS IN ENVIRONMENTAL SAMPLES BY MULTICOLLECTOR ICP/MS
[Poster]
Berni, Alex; Baschieri, Carlo; Marchetti, Andrea; Durante, Caterina; Covelli, Stefano; Emili, Andrea; Manzini, Daniela
abstract
Mercury isotopes can be an effective tool to investigate about the biogeochemical cycle of Hg, in order to
distinguish among different sources and prevent its well-known pollution in environment and food webs.
In this work, we set up a method for Hg isotopic ratio determination by multicollector ICP-MS
spectrometry by using a cold vapour generator system (CVG). Basically, the system permits to get
measures independent from any matrix effects achieving high precisions and sensitivities. The method
was optimized by Design of Experiment (DoE) technique to minimize inner uncertainty on isotopic
ratios. Instrumental mass bias on measures was accounted by simultaneously monitoring 205Tl/203Tl from
the isotopic SRM NIST 997 and applying the correction algorithm proposed by Yang and Sturgeon.
The method repeatability and reproducibility were evaluated for a two years period on a large data set
built by measuring the NIST 3133 standard solution with an Hg concentration of 20 ng g-1 for more than
500 times. Hg isotope ratios (expressed as mean ± 2 standard deviations), are comparable with those of
others works for all the monitored species, namely 199Hg/198Hg = 1.6881 ± 0.0006, 200Hg/198Hg = 2.3061
± 0.0011, 201Hg/198Hg = 1.3139 ± 0.0014 and 202Hg/198Hg = 2.9635 ± 0.0014.
Precisions and sensitivities of the method are fit for purpose to investigate fractionation phenomena, mass
dependent (MDF) and mass independent (MIF), for Hg that might occur during the uptake processes of
the element and its derivatives in living organisms.
2014
- Mercury isotopes to explore sources and fate of Hg in the environment: the case study of the Augusta Bay (southern Italy)
[Relazione in Atti di Convegno]
Bonsignore M., Tamburrino S.; Marchetti, Andrea; Durante, Caterina; Berni, Alex; Mazzola, S.; Sprovieri, M.
abstract
The Augusta Bay is a nearly closed marine basin located on the southeastern coast of Sicily (southern Italy) which has suffered, since the early 60s, the effect of the uncontrolled chemical discharge of Hg from the most important chlor-alkali plant in Italy (Le Donne and Ciafani, 2008), resulting in high Hg concentrations in sediments, seawater, atmosphere and fishes (Bagnato et al., 2013; Bonsignore et al., 2013; Sprovieri et al., 2001; Ficco et al., 2009; ICRAM, 2005; Ausili et al., 2008; Environ International Team, 2008; Di Leonardo et al., 2007, 2008). For the first time, here we report the results obtained by the measurements of mercury isotopes in sediments, fish muscles and human hair of resident populations, in order to trace sources of Hg and processes driving the biogeochemical cycle of this metal in the environment. Actually, Hg stable isotopes demonstrated an excellent tool for identifying sources and transformation processes of this element in different environmental compartments. Specifically, a positive relationship (r2=0.94; slope: 1.07±0.01) was found between Δ201Hg and Δ199Hg (MIF) for all the environmental matrices coming from the Augusta Bay. This primarily suggests the crucial link between the main Hg source in the Augusta Bay (sediment) and the final receptor (the man) related to fish consumption. Sediments display MIF (expressed as Δ201Hg and Δ199Hg) close to zero and negative MDF (expressed as δ202Hg) that we consider biologically mediated MeHg production. The lower δ202Hg values recorded in the southern area of the basin demonstrated the higher microbial activity occurred just in the zone with the highest mercury concentration in sediments. Furthermore, MIF fractionations in fishes plot on a single line (r2=0.84; slope 1.00±0.03) clearly testifying photochemical reduction of Hg (II) prior of the intake in the marine food web. Moreover, Hg fractionates according to fish ecology with MIF and MDF higher in pelagic fishes and lower ratios in demersal and benthic species. This observation suggests crucial effects of Hg(II) photoreduction processes in surface waters and relevant effects of microbial methylation in the deeper part of the basin. Finally, hair samples show a positive relationship on the base of Δ201Hg and Δ199Hg comparison (r2= 0.93; slope 1.00±0.14) and that we ascribe to the effects of photoreduction of Hg(II) in presence of organic substances. The role of sediments as primary source of Hg for the marine biotic compartment is testified by the overlapping δ202Hg values in fishes and sediments, while the 2‰ difference in δ202Hg values between fishes and hair samples appears consistent with a metabolic fractionation (Laffont et al., 2009).
2014
- Tracing environmental pollution processes in aquatic systems by Hg isotope ratio determination
[Abstract in Atti di Convegno]
Berni, Alex; Baschieri, Carlo; Durante, Caterina; Rossi, Maria Cecilia; Manzini, Daniela; Emili, Andrea; Rampazzo, F.; Berto, D.; Fortibuoni, T.; Noventa, S.; Covelli, Stefano; Marchetti, Andrea
abstract
Mercury stable isotopes are an excellent tool to distinguish among different sources of
this element and to investigate its transformation processes in environmental
compartments and in food webs. To do this, an highly precise and sensitive method
was set up by using a cold vapor generator system (CVG) to introduce gaseous Hg0
into a multicollector ICP-MS spectrometer[1], allowing “dry plasma” measurement
conditions to minimize any matrix effect on the obtained results. Instrumental mass
bias on measures was accounted by simultaneously monitoring 205Tl/203Tl from the
isotopic SRM NIST 997 and applying the correction algorithm proposed by Yang and
Sturgeon[2].
This method was applied to the case study of Grado and Marano Lagoon, Italy and of
the northern Adriatic Sea. The lagoon has been subjected to Hg input from both
industrial waste (chlor-alkali plant) and residues of long-term mining activity (Idrija
mine, NW Slovenia) transported by the Isonzo river and marine currents[3].
Mercury isotopic ratios detected on sediments, fish and mollusk tissue samples show
both mass-dependent (MDF) and mass-independent (MIF) fractionation phenomena
for Hg. With these data, it has been possible to gain a more detailed characterization of
the Hg input sources in the lagoon and to gather information on the uptake processes
of the element and its derivatives in living organisms.
2013
- Application of data fusion techniques to direct geographical traceability indicators
[Articolo su rivista]
Silvestri, Michele; Bertacchini, Lucia; Durante, Caterina; Marchetti, Andrea; Salvatore, Elisa; Cocchi, Marina
abstract
A hierarchical data fusion approach has been developed proposing multivariate curve resolution (MCR) as a variable reduction tool.
The case study presented concerns the characterization of soil samples of the Modena District. It was performed in order to understand, at a pilot study stage, the geographical variability of the zone prior to planning a representative soils sampling to derive geographical traceability models for Lambrusco Wines. Soils samples were collected from four producers of Lambrusco Wines, located in in-plane and hill areas. Depending on the extension of the sampled fields the number of points collected varies from three to five and, for each point, five depth levels were considered.
The different data blocks consisted of X-ray powder diffraction (XRDP) spectra, metals concentrations relative to thirty-four elements and the 87Sr/86Sr isotopic abundance ratio, a very promising geographical traceability marker.
A multi steps data fusion strategy has been adopted. Firstly, the metals concentrations dataset was weighted and concatenated with the values of strontium isotopic ratio and compressed. The resolved components described common patterns of variation of metals content and strontium isotopic ratio. The X-ray powder spectra profiles were resolved in three main components that can be referred to calcite, quartz and clays contributions. Then, a high-level data fusion approach was applied by combining the components arising from the previous data sets.
The results show interesting links among the different components arising from XRDP, the metals pattern and to which of these 87Sr/86Sr Isotopic Ratio variation is closer. The combined information allowed capturing the variability of the analyzed soil samples.
2013
- DATA FUSION APPROACH FOR THE VARIETAL CLASSIFICATION OF LAMBRUSCO P.D.O. WINES
[Relazione in Atti di Convegno]
Cocchi, Marina; Silvestri, Michele; Salvatore, Elisa; Elia, A.; Durante, Caterina; Marchetti, Andrea; Papotti, Giulia; Bertelli, Davide; Plessi, Maria
abstract
Owing to the increasing of the throughput of modern analytical techniques and the needs of getting exhaustive information on the peculiarities of similar samples in terms of composition for both authenticity and geographical or varietal origin purposes, it is necessary to extract hidden information from complex data set.
The possibility to jointly analyze data sets arising from different sources (e.g. different analytical determinations/platforms) allows capturing the latent information that would not be extracted by the individual analysis of each block of data. Several approaches are proposed in the literature and are generally referred to as data fusion ones. In this work a hierarchical data fusion is proposed [1,2] for the characterization of three varieties of Lambrusco Wine (Salamino di Santa Croce, Grasparossa di Castelvetro, Sorbara), a typical P.D.O. product of the District of Modena (Italy). In particular, 60 wine samples of the three different varieties were analyzed by means of HPLC-DAD fro the phenolic compounds evaluation, Emission- Excitation Fluorescence Spectroscopy and 1H-NMR.
Since the analytical outputs are characterized by different dimensionality (matrix and tensor), several multivariate analysis were applied (PCA, PARAFAC, MCR-ALS) in order to extract and merge, in a hierarchical way, the information present in each data set.
Results showed that this approach was able to well characterize Lambrusco samples giving also the possibility to understand the correlation between the source of information arising from the three analytical techniques.
2013
- DETERMINATION OF PHENOLIC COMPOUNDS AND AUTHENTICATION OF PDO LAMBRUSCO WINES BY HPLC-DAD AND CHEMOMETRIC TECHNIQUES
[Articolo su rivista]
Salvatore, Elisa; Cocchi, Marina; Marchetti, Andrea; Federico, Marini; Anna De, Juan
abstract
This work proposes a fast and simple method for detection and quantification of phenolic compounds in P.D.O. Lambrusco wines using HPLC-DAD and chemometric techniques.
Samples belonging to three different varieties of Lambrusco (Grasparossa, Salamino and Sorbara) were analyzed to provide a methodology appropriate for routine analysis. Given the high complexity of the sample and the coelution among chromatographic peaks, the use of chemometric techniques to extract the information of the individual eluting compounds was needed. Multivariate Curve Resolution - Alternating Least Squares (MCR-ALS) allowed the
resolution of the chromatographic peaks obtained and the use of this information for the quantification of the phenolic analytes in the presence of interferences. Use of multiset analysis and local rank/selectivity information was proven to be crucial for the correct resolution and quantification of compounds. The quantitative data provided by MCR-ALS about the phenolictargets and additional compounds present in the samples analyzed provided wine composition profiles, which were afterwards used to distinguish among wine varieties. Principal ComponentAnalysis applied to the wine profiles allowed characterizing the wines according to their varieties.
2013
- ENHANCING CONSUMER QUALITY PERCEPTION TOWARDS PROTECTED DESIGNATION OF ORIGIN PRODUCTS BY GEOGRAPHICAL TRACEABILITY: THE CASE OF BOLOGNA POTATOES PDO
[Abstract in Atti di Convegno]
Bertacchini, Lucia; Durante, Caterina; Marchetti, Andrea; Silvestri, Michele; Tassi, Lorenzo
abstract
The development of analytical methodologies able to confirm/determinate the geographic origin of food is becoming an increasingly dynamic area in authenticity as well as traceability context.
The globalization of agri-food system led to the spread of different varieties of food and raw materials around the world but sometimes also to a loss in their quality. Therefore, geographical origin of food often became synonymous of quality and safety and its authentication remains an important goal for producers and consumers too.
Aim of this study is to develop a geographical traceability model for a typical food of Bologna district, namely the Bologna PDO potatoes. The product obtained the designation of origin in 2009 and according to the respective European Regulation [1], its production can be obtained from a variety, ‘Primura’, grown in soils of Bologna district. In particular, in this study, among the different geographical indicators, strontium isotopic ratio, 87Sr/86Sr, has been used, given to its tracer potentialities able to link a food to its territory of origin [2]. Thanks to the collaboration with the Consortium of the potato producers of Emilia Romagna (ASSOPA), within a project funded by Emilia Romagna region [3], samples of potato tubers of two varieties (‘Agata’ and ‘Primura’), harvested in 2012, and soils (0–20 cm depht) were collected in different cultivated areas of Emilia Romagna. In particular, three different geological substrates soils were considered: "Alluvional Plain of the Appennine Rivers" (Bologna, Ravenna), "Po Plain" and "Coastal Plain" (Ferrara). All sampling sites were chosen on the basis of productivity and availability of the farmer criteria.
87Sr/86Sr values in potatoes and soils samples have been determined by using a double focusing magnetic sector multicollector. The isotopic values obtained for potatoes perfectly matched with their respective soils in almost all the cases. Furthermore, the used indicator was able to discriminate samples coming from lowlands and the Emilia Romagna’s coast. Nevertheless, more work is needed, such as the careful understanding of the impact of agricultural practices (e.g. conditions of use of fertilizers and of irrigation water) and the validation of model with the analysis of samples coming outside the Bologna district.
2013
- Geographical traceability based on 87Sr/86Sr indicator: A first approach for PDO Lambrusco wines from Modena
[Articolo su rivista]
Durante, Caterina; Baschieri, Carlo; Bertacchini, Lucia; Cocchi, Marina; Sighinolfi, Simona; Silvestri, Michele; Marchetti, Andrea
abstract
The main goal of this study was to evaluate 87Sr/86Sr ratio in different matrices, namely soils, branches,
and grape juices, of an oenological food chain in order to develop a robust analytical strategy able to link
the investigated food to its territory of origin. The 87Sr/86Sr has been used as traceability marker and several
aspects, affected its variability, i.e. geological features of the investigated area, the bio-available fraction
of elements in the soils and the up-take of the plant, have been taken into account. Optimisation of
an analytical procedure for the separation of Sr from its interferences and investigation of the analytical
performances in terms of precision of used methodology have been carried out as well. This work highlighted
a good match between the isotopic values monitored in the bio-available fraction of soils and
their respective grape juices for almost all the investigated areas. The correlation with food satisfyingly
improves when isotopic relative abundance values of branches vine are considered.
2013
- Mercury isotope ratios as contamination markers: procedure development and applications
[Abstract in Atti di Convegno]
Berni, Alex; Baschieri, Carlo; Durante, Caterina; Marchetti, Andrea; Bertacchini, Lucia; Covelli, Stefano; Petrini, Riccardo; Tassi, Lorenzo; Emili, Andrea; Manzini, Daniela
abstract
Mercury, Hg, is one of the most harmful elements present in the Earth, and has both natural and
anthropological sources. Moreover, Hg undergoes many different transformation pathways during
its biogeochemical, or industrial, cycles which in general involve redox reactions, both abiotic and
biotic, and phase changes. Despite the toxicity of this pollutant, there is still a lack in the
knowledge about its biogeochemistry in the ecosystem and, therefore, it is of utmost relevance to
develop new scientific approaches to deepen its transformation mechanisms and to identify the
contamination sources. In this context, the determination of mercury stable isotopes ratios seems to
be an extremely interesting and challenging application to verify the “provenance” of the element,
i.e. to identify whether it is of natural or anthropogenic source. This approach can be useful in case
of polluted areas where many are the contamination sources in order to plan an environmental
requalification, as in the present case study represented by the National Interest Site of the lagoon of
Marano-Grado (Trieste, Italy), which is the main object of the present investigation.
2013
- RP-HPLC and Chemometrics for wheat flour protein characterization in an industrial bread-making process monitoring context
[Articolo su rivista]
LI VIGNI, Mario; Baschieri, Carlo; Marchetti, Andrea; Cocchi, Marina
abstract
In the baking industry, a difficult task is to keep the quality perceived by the consumer as constant as possible, given the inner variability of flour, e.g. due to different wheat mixtures, harvesting time, etc. Here, we evaluated the influence of flour batches properties on bread quality, considering an industrial bread making process. In particular, flour composition in terms of protein fractions (gliadins, glutenins) has been determined by means of RP-HPLC, to assess the inter- and intra-batch variability of flour mixtures deliveries at a baking plant. Multivariate data analysis allowed evaluation of correlation between flour protein composition and technological properties. A great variability within different deliveries of a same flour batch emerged, as well as a considerable seasonal variability. Correlation models among protein sub-fractions, technological properties and bread quality are difficult to establish; however, the role of the protein profile on flour behaviour in bread making could be highlighted.
2013
- Soils sampling planning in traceability studies by means of experimental design approaches
[Articolo su rivista]
Totaro, Sara; Coratza, Paola; Durante, Caterina; Foca, Giorgia; LI VIGNI, Mario; Marchetti, Andrea; Marchetti, Mauro; Cocchi, Marina
abstract
The present research is part of a project dealing with the development of analytical methodologies mainly based on primary indicators, such as isotopic ratio of radiogenic elements, for theauthenticity and geographical traceability of oenological food, typical of the Modena district. In particular, considering the objective of establishing a food-territory link by means of these analytical indicators, it is straightforward how the representativeness of sampling for both food and soils, covers a primary role in the robustness of the traceability models. With the aim of building traceability models for oenological matrices, the issue of selecting a set of representative, informative and different soil samples is tackled. In this case, the goal is not obtaining a set of soil samples uniformly spanning the territory to be investigated, since the planning of a punctual sampling extended in the whole district of Modena is not feasible considering the total number of samples affordable by the study, but rather to choose a representative set of vineyards were to locate the soil samples. Thus, all the vineyard-registered producers of the district of Modena were considered and different variables (geological features of the soils, winegrowing coverage, grapes varieties, yearly productions of the farms, etc.) were handled with Experimental Design (DoE) techniques in order to simultaneously taking into account the different kinds of information for achieving a sustainable and rational site sampling. In particular, D-Optimal Onion design was chosen since it is widely used for mapping and planning purposes, hence it consents to achieve the maximum coverage and uniformity of the selected samples in the whole domain. An efficient mapping of geographical region has been obtained ensuring coverage of farms characterized by main grape production and insisting on soils with different geological features.
2013
- TERROIR DIFFERENTIATION OF LAMBRUSCO PDO WINES BY STRONTIUM ISOTOPIC SIGNATURE
[Relazione in Atti di Convegno]
Baschieri, Carlo; Berni, Alex; Bertacchini, Lucia; Cocchi, Marina; Durante, Caterina; Vigni, M. Li; Manzini, Daniela; Marchetti, Andrea; Sighinolfi, Simona
abstract
The interest of consumers, as well as of producers, toward origin and quality of food has increased over the last years. As regards the oenological field, the quality of wine is in many cases related to the concept of terroir (history, geographical origin, typical raw materials and methods, ecc.). In this context, the assessment of the link between the territory of origin and the food product by means of analytical indicators represents a challenging target, useful for the valorization of the product itself. Among the different indicators used for geographical traceability studies, the 87Sr/86Sr isotopic ratio (Sr-I.R.), has provided excellent results for different types of food.
The present research is part of a project dealing with the development of authenticity and geographical traceability models of PDO Italian wines [1], with particular reference on Lambrusco wines, which are one of the main typical products of the Modena district. The possibility of obtaining reliable traceability models is mainly linked to the capability of monitoring the considered indicator in a representative set of investigated matrices: mainly soil and wines. Thanks to the collaboration with Consorzio Marchio Storico dei Lambruschi Modenesi, it has been possible to measure the Sr-I.R. on a statistically representative set of Lambrusco wines, commercially available and produced in 2010, 2011 and 2012. Furthermore, Sr-I.R. values of wines were compared with the Sr-isotopic ranges of Modena soils, with the aim to verify and establish a link with the respective territory of origin. The selection of representative, informative and different soil samples of the Modena district was accomplished in a previous work by means of Design of Experiment techniques, in order to ensure a sustainable and rational mapping of the investigated geographical area, taking into account properties related to geological features and production variables (grape varietals and produced quantities) [2]. Finally, the Sr-I.R. was also determined on vine branches, collected in proximity of each soil sampling point, since previous researches highlighted an improvement of the correlation with food and a better discriminating power, when considering branches instead of soil [3].
2013
- THE ROLE OF MASS FRACTIONATION PROCESSES IN Hg ISOTOPE RATIOS MEASUREMENTS
[Relazione in Atti di Convegno]
Baschieri, Carlo; Berni, Alex; Bertacchini, Lucia; Durante, Caterina; Silvestri, Michele; Marchetti, Andrea; Covelli, S.; Emili, A.; Rossi, Maria Cecilia
abstract
Among the global pollutants, Mercury could be considered one of most harmful. For this reason, the study of the distribution and of the sources of this element is relevant for the aims of environmental protection and the human health safeguard. In these contexts, the determination of mercury stable isotopes ratios and, in particular, the identification and the study of fractionation processes seems to be an extremely interesting and challenging field of investigation to verify the “provenance” of the element. Mercury, in fact, undergoes to both mass dependant, MDF, and mass independent fractionation, MIF, processes. In particular the MIF, involving only the odd isotopes (199Hg and 201Hg), appears to be a characteristic fingerprint of the process and the pathways involved in the Hg transformations [1]. Thus, the study of both fractionation phenomena can be a powerful tool to identify its natural or anthropogenic source. In order to have the required precision, the determination of the Hg isotope ratios is commonly conducted by means of HR-MC-ICP/MS instruments. The low magnitude of the MDF and MIF makes the correction of the instrumental mass-bias (MB) a critical step in the determination chain. The most common method for the MB correction assumes an exponential fractionation law and uses for the normalization the Tl isotope ratio [2]. The use of a different element for the MB correction could introduce some errors in the correction step, due to different factors such as the high difference in mass between the normalization couple and the corrected ratio (205Tl/203Tl for 199Hg/198Hg) and differences in the MB factors of the two elements. In order to minimize the possible errors in the correction step, for the Hg some authors report different applications of the exponential law to the MB problem [3]. The evaluation of the influence of the different methods on the data was conducted applying them on the same dataset and comparing the results with the values reported in literature. The dataset was composed by standards (NIST SRM3133) acquired in different session of measurement and coming from the bracketing sequences. Moreover, the influence of the sample matrix and sample preparation technique on the fractionation processes was also investigated acquiring the Hg ratios of muscle samples spiked with the SRM3133 at different concentration.
2013
- The impact of chemometrics on food traceability
[Capitolo/Saggio]
Bertacchini, Lucia; Cocchi, Marina; LI VIGNI, Mario; Marchetti, Andrea; Salvatore, Elisa; Sighinolfi, Simona; Silvestri, Michele; Durante, Caterina
abstract
In the last decades, mankind has become totally aware about the importance of food quality: nowadays authentication and traceability are words of general use.
Food authentication verifies how much a food is in accordance with its label description and law and it could be considered a further guarantee for the quality and safety of a foodstuff.
The traceability of food could be considered an essential element in ensuring safety and high quality of food. The synergistic use of instrumental analytical techniques and chemometrics represents a promising way to obtain trustworthy results in the development of authenticity and traceability models. This chapter deals with the potentialities of chemometrics tools in resolving some real issues related to food traceability and authenticity. Particular attention will be paid to the use of some exploratory, classification and discrimination techniques.
In the first part of this chapter, a briefly description of European regulations (Authenticity and Traceability: the European Union point of view), and traceability and authenticity markers (Authenticity and Traceability: a scientific point of view) is reported. The second part is split into two sections: namely Food Authenticity and Food Traceability applications, where the main features and advantages of some chemometrics approaches are presented.
2012
- Characterization of lambrusco wines by means of Sr isotope ratio as provenance marker
[Abstract in Rivista]
Baschieri, Carlo; Bertacchini, Lucia; Cocchi, Marina; Marchetti, Andrea; Durante, Caterina; Bertelli, Davide; Papotti, Giulia; Sighinolfi, Simona
abstract
Recently, geographical origin and authenticity of food are topics of great interest for consumers as well as for producers in the food industry. Furthermore, in the oenological field, these concepts are strictly tied with the quality of food. For different reasons, people are more focused towards food characterized by a well-established geographical origin. In the course of time, the symbiosis of
quality and the geographical origin of products is certainly related to ethics of the producers and the whole determines the reputation of the territory. The present research is part of a project dealing with the development of authenticity and geographical traceability models of Italian wines, with particular reference on Lambrusco wines, which are one of the main typical products of the Modena district. Among the different indicators used for traceability studies, 87Sr, and in particular the 87Sr/86Sr isotopic ratio (I.R.), has provided excellent results for different types of food matrices. Aim of this work is to obtain a reliable fingerprint for Lambrusco
wine on the basis of its 87Sr/86Sr isotopic value, linking it to its territory of provenance. Moreover, different analytical methods for the elimination of matrix interferences, before the Sr/Rb separation on resin, are also tested. In particular, the first method, widely used in literature, consists of the following step: i) ethanol elimination by means of HNO3 addition and ii) sample digestion through microwave assisted in acidic media. While, the second one merely consists in the addition of an aliquot of HNO3. Finally, as a preliminary study, wine samples were pre-treated according to the best procedure and 87Sr/86Sr measurements were accomplished
with an high resolution multicollector inductively coupled plasma mass spectrometry (HR-MC-ICP-MS). The isotopic data of wines were compared with the isotopic range of Modena soils, with the aim to determine a correlation between soil and food, obtaining promising results as far as the potentiality of 87Sr/86Sr as geographical tracer is concerned. To the authors’ knowledge, this is the first report developing an easy analytical methodology for the pretreatment of the studied matrix, obtaining high precision and accuracy measurements, in terms of repeatability, reproducibility and time variability of the monitored indicator.
2012
- MERCURY ISOTOPE RATIOS AS CONTAMINATION MARKERS:
PROCEDURE DEVELOPMENT AND APPLICATIONS
[Abstract in Rivista]
Baschieri, Carlo; Durante, Caterina; Marchetti, Andrea; Berni, Alex; Bertacchini, Lucia; Stefanocovelli, ; Petrini, Riccardo; Emili, Andrea; Tassi, Lorenzo
abstract
Mercury is one of the most harmful elements present in the Earth, and has
both natural and anthropological sources. Moreover, Hg can undergo to
many different transformation pathways during its biogeochemical, or
industrial, cycles which in general involve redox reaction, both abiotic and
biotic, and phase changes (1). Despite the toxicity of this pollutant, there is
still a lack in the knowledge about the biogeochemistry of mercury in the
ecosystem and, therefore, it is of utmost relevance to develop new scientific
approaches to understand its transformation mechanisms and to identify its
contamination sources. In this context, the determination of mercury stable
isotopes ratios and, in particular, the identification of fractionation processes
seems to be an extremely interesting and challenging application to verify
the “provenance” of the element. Mercury, in fact, undergoes to both mass
dependant, MDF, and mass independent fractionation, MIF, processes. In
particular the MIF, involving only the odd isotopes (199Hg and 201Hg),
appears to be a characteristic fingerprint of the process and the pathways
involved in the Hg transformations (2). Thus, the study of both fractionation
phenomena can be a powerful tool to identify its natural or anthropogenic
source. This approach can be useful in case of polluted areas where many
are the contamination sources in order to plan an environmental
requalification. An intriguing case study is represented from the National
Interest Site of the lagoon of Marano-Grado (Trieste, Italy), which is object
of the present study. For these purposes, the evaluation of the isotopic
composition in samples coming from this area has been performed by means
of an HR-MC-ICP/MS system for the simultaneous determination of all the
isotopes of interest (3). Due to the difficulties of the mercury ICP
determination and the high number of the acquisition parameters the
optimization and the validation of the analytical procedure was required, in
order to obtain highly accurate and precise data. After this first step the
method has been applied for the determination of the Hg isotopic
fingerprints in environmental samples (e.g. sediments) coming from the
Marano-Grado area.
(1) W. Fitzgerald, C. Lamborg, Treatise on Geochemistry 9, Elsevier, 2004.
(2) B. Bergquist, J. Blum, Elements, (2010), 353-357.
(3) D. Foucher, H. Hintelmann, Anal. Bioanal. Chem., (2006), 1470-1478.
2012
- Mercury Isotope Ratios as Contamination Markers: Procedure Development and Application
[Abstract in Atti di Convegno]
Baschieri, Carlo; Durante, Caterina; Marchetti, Andrea; Bertacchini, Lucia; Berni, Alex; Covelli, Stefano; Petrini, Riccardo; Emili, Andrea; Manzini, Daniela
abstract
Mercury is one of the most harmful elements present in the Earth, and has both natural and anthropological sources. Moreover, Hg can undergo to many different transformation pathways during its biogeochemical, or industrial, cycles which in general involve redox reaction, both abiotic and biotic, and phase changes (1). Despite the toxicity of this pollutant, there is still a lack in the knowledge about the biogeochemistry of mercury in the ecosystem and, therefore, it is of utmost relevance to develop new scientific approaches to understand its transformation mechanisms and to identify its contamination sources. In this context, the determination of mercury stable isotopes ratios and, in particular, the identification of fractionation processes seems to be an extremely interesting and challenging application to verify the “provenance” of the element. Mercury, in fact, undergoes to both mass dependant, MDF, and mass independent fractionation, MIF, processes. In particular the MIF, involving only the odd isotopes (199Hg and 201Hg), appears to be a characteristic fingerprint of the process and the pathways involved in the Hg transformations (2). Thus, the study of both fractionation phenomena can be a powerful tool to identify its natural or anthropogenic source. This approach can be useful in case of polluted areas where many are the contamination sources in order to plan an environmental requalification. An intriguing case study is represented from the National Interest Site of the lagoon of Marano-Grado (Trieste, Italy), which is object of the present study. For these purposes, the evaluation of the isotopic composition in samples coming from this area has been performed by means of an HR-MC-ICP/MS system for the simultaneous determination of all the isotopes of interest (3). Due to the difficulties of the mercury ICP determination and the high number of the acquisition parameters the optimization and the validation of the analytical procedure was required, in order to obtain highly accurate and precise data. After this first step the method has been applied for the determination of the Hg isotopic fingerprints in environmental samples (e.g. sediments) coming from the Marano-Grado area.
2012
- Use of X-Ray Diffraction Technique and Chemometrics to aid Soil Sampling strategies in traceability studies
[Articolo su rivista]
Bertacchini, Lucia; Durante, Caterina; Marchetti, Andrea; Sighinolfi, Simona; Silvestri, Michele; Cocchi, Marina
abstract
Aim of this work is to assess the potentialities of the X-ray powder diffraction technique as fingerprinting technique, i.e. as a preliminary tool to assess soil samples variability, in terms of geochemical features, in the context of food geographical traceability. A correct approach to sampling procedure is always a critical issue in scientific investigation. In particular, in food geographical traceability studies, where the cause–effect relations between the soil of origin and the final foodstuff is sought, a representative sampling of the territory under investigation is certainly an imperative. This research concerns a pilot study to investigate the field homogeneity with respect to both field extension and sampling depth, taking also into account the seasonal variability. Four Lambrusco production sites of the Modena district were considered. The X-Ray diffraction spectra, collected on the powder of each soil sample, were treated as fingerprint profiles to be deciphered by multivariate and multi-way data analysis, namely PCA and PARAFAC. The differentiation pattern observed in soil samples, as obtained by this fast and non-destructive analytical approach, well matches with the results obtained by characterization with other costly analytical techniques, such as ICP/MS, GFAAS, FAAS, etc. Thus, the proposed approach furnishes a rational basis to reduce the number of soil samples to be collected for further analytical characterization, i.e. metals content, isotopic ratio of radiogenic element, etc., while maintaining an exhaustive description of the investigated production areas.
2011
- DISTRIBUTION OF HEAT STABILIZERS IN PLASTICIZED PVC-BASED BIOMEDICAL DEVICES: TEMPERATURE AND TIME EFFECTS
[Articolo su rivista]
Lidia Maria, Bodecchi; Durante, Caterina; Marcello, Malagoli; Manfredini, Matteo; Marchetti, Andrea; Sighinolfi, Simona
abstract
Thermoplastic polymers can be viewed as a dynamic framework in which additives allocation is strongly dependent on the system’ chemistry. Considering the complexity of the distribution phenomena that may occur in plastics obtained by blending polymeric resins with different additives, this work constitutes an attempt to the description of the behavior of PVC heat stabilizers (calcium and zinc carboxylates), as regard temperature and time. Thanks to the Fourier Transform Infrared Spectroscopy, it is possible to observe a first decreasing trend of the additives related IR-bands as a function of the increasing temperature and the higher the temperature the faster the decrease of the heat stabilizers intensities bands is, with respect to time. Additives distribution in not sterilized, sterilized, aged not sterilized and aged sterilized materials have been investigated to determine their behavior with respect to temperature, from 30 to 120 0C, and time. A simulated supplementary aging process equivalent to 9 months aging was carried out on aged not sterilized and aged sterilized materials to gain more data on the transport/reaction phenomena these additives in the plastic material.Experimental evidences allow hypothesizing that reaction and redistribution phenomena probably concur to determine the additives allocation in PVC as a function of temperature and time.
2011
- Evolution of 5-(hydroxymethyl)furfural and furfural in the production chain of the aged vinegar Aceto Balsamico Tradizionale di Modena
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; P., Lambertini; Manzini, Simona; Marchetti, Andrea; Sighinolfi, Simona; Totaro, Sara
abstract
The present investigation focuses on the monitoring of furfurals along the production chain of the agedvinegar Aceto Balsamico Tradizionale di Modena, from the starting raw material to the final product, inorder to control the quality and safety of this food. In particular, the aim of the study is to achieve a reductionin the furfurals content and, therefore, an optimised heating procedure for the starting grape juicewas proposed and compared to that which is currently adopted. 5-(Hydroxymethyl)furfural (HMF) andfurfural were determined by HPLC. Results show that the suggested heating procedure leads to a decreaseof furfurals in the cooked must. In addition, for comparison purposes, HMF and furfural were also measuredduring the ageing phase of the vinegar and in the final marketable products as well.
2011
- L'Aceto Balsamico Tradizionale di Modena secondo Francesco Aggazzotti
[Commento scientifico]
Marchetti, Andrea
abstract
Il ruolo e l’importanza del pensiero di Francesco Aggazzotti del Colombaro emerge chiaramente attraverso l’attenta analisi del suo operato nei diversi ambiti, politico, agronomico, sociale e culturale. Sarebbe certamente riduttivo tracciare un profilo dell’illustre avvocato modenese unicamente e solamente a partire dalla lettera inviata al collega Pio Fabriani nel marzo del 1862 nella quale l’Aggazzotti descrive, con dovizia di dettagli, la procedura operativa per la preparazione dell’Aceto Balsamico Tradizionale di Modena, ABTM, (secondo l’attuale denominazione) oltre a fornire cenni sulle modalità di conduzione dell’acetaia, in quanto il contributo fornito nel solo ambito agronomico fu certamente maggiore.
2011
- Microwaves: theoretical and practical aspects
[Capitolo/Saggio]
Marchetti, Andrea; Sighinolfi, Simona
abstract
The wave-matter interaction mechanisms lies beyond the possibility of heating materials and substances by microwaves. A deep knowledge of these processes certainly represents a valuable aspect for a better and safer use of this “sample preparation analytical technique”. With these aims, the following sections will illustrate the starting working principles of microwave: namely the theory, highlighting all the features of the energy dissipation in the materials.
2011
- Microwaves: theoretical aspects and practical applications in chemistry
[Curatela]
Marchetti, Andrea; Elia, Boffelli; Pilar Bermejo, Barrera; Betarice, Bocca; William, Maher; Caterina, Durante; M. D., Luque de Castro; Joaquim A., Nobrega
abstract
The introduction of new technologies contributes, in many cases, in the rapid changing in the way we live, learn and work. This also happened with the introduction of devices based on microwave technologies, which nowadays range from communication tools to the more common heating apparatus. In this context we can certainly assess that microwaves deeply changed the way we were. Furthermore, microwaves changed, and will still change, the way we communicate each other and work. We should be aware of this fact.Since the appearance of the first lab application, dated 1975, microwaves helped the chemists to reduce the time needed in the sample preparation, on one hand, and opened a series of new frontiers characterized by new research perspectives and knowledge on the other one.As a matter of fact, the most relevant and important acquisition with the introduction of microwaves was that people, for the first time, were able to supply and control, under certain conditions, the energy involved in reactions. Probably this was not exactly the situation at the beginning but today the new microwave devices can deliver electromagnetic radiation “when needed”. In turns, this means safer procedures and more accurate and precise analytical data. The aims of this book are mainly focused on the microwave digestion and extraction topics. State of the art examples and a deep critical discussion of the reported data are the common denominator of all the scientific contributes.Sample treatment has become an integral and fundamental part in the development process of analytical methods. Several different fields, such as physics, chemistry, geology, pharmaceutical science, nuclear science, material science, cosmochemistry, archeology, petroleum industry, pharmaceutical chemistry, forensic science, and environmental science, have benefited from the highly productive capabilities in sample preparation of this analytical technique. With the expansion of activities in instrumental analytical determinations, an impressing need is felt for time saving procedures. As far as the topics of the book are concerned, these are intended to fulfill the need of providing a well-balanced and in-depth discussion of the basic concepts and latest developments over a range of important subjects in modern sample treatment techniques by means of microwave heating devices.The idea for a new book on microwave topics was born some time ago and started from the consideration that in literature was missing a “manual” that, starting from a solid and detailed discussion on the basic principles of the wave-matter interactions, could also be used as an “operative manual” reporting the state of the art of the scientific knowledge in this field, even if excellent and valuable books are still available such as “Microwave Sample Preparation: theory and practice”, edited by H.M. (Skip) Kingston and Lois B. Jassie (1988), and “Microwave-Enhanced Chemistry: fundamentals, sample preparation and applications”, edited by H.M. (Skip) Kingston and Stephen J. Haswell (1997). Therefore, following this approach the eight chapters, which this book is constituted of, give an account of the experiences and knowledge of several Authors within this area.The material in the book has evolved from the teaching and working experiences of the researchers involved.In particular, chapter 1 deals with the description of the fundamental molecular processes, which lie behind the interaction between electromagnetic waves and the matter in the microwaves region responsible of the heating phenomena.Chapter 2 gives an overview of the chronological evolution of several MW devices with an emphasis on the vessels and pressure /temperature control apparatus.Chapters from 3 to 5 describe, with plenty of details, the multiple use and applications of the MW energy in several area and the recent results in the biological field for the trace and ultra trace element determinat
2011
- Modelling of Experimental Thermophysical Data by Mixing of a Ternary Solvent System
[Capitolo/Saggio]
Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Thermomechanic and thermodynamic properties of mixing solvents in the liquid state have proven a powerful tool in elucidating the specific interactions and structural features supporting the liquid structure in multicomponent nonelectrolytic solutions. Mass transport properties (density, viscosity), thermophysical properties (relative permittivity, refractive index), and related thermodynamics can deepen elucidate the solvent – solvent specific interactions and behavioural peculiarities of the complex real systems. In this paper, we will primarily deal with the experimental measurements and correlative studies both on temperature and composition, of the above mentioned properties (Y), working with a ternary solvent system containing 1,2-ethanediol (ED), 2-methoxyethanol (ME) and 1,2-dimethoxyethane (DME), at various temperatures in the range -10 £ t (°C) £ 80, and with different compositions covering the whole miscibility field of the selected species. These components are strictly parent species, all being 1,2-ethanedyil-derivatives (-CH2-CH2-), pertaining to the amphiphile class molecules, with different balancing degree of hydrophobic and hydrophilic properties. Furthermore, the excess properties (YE) and deviation functions (DY) are largely stressed and examined along the text in order to identify the presence of solvent – cosolvent adducts in these ternary mixtures.
2011
- Monitoring Flour Performance in Bread Making
[Capitolo/Saggio]
LI VIGNI, Mario; Baschieri, Carlo; Foca, Giorgia; Marchetti, Andrea; Ulrici, Alessandro; Cocchi, Marina
abstract
A methodology to monitor flour performance in industrial bread-making based on evaluation of rheological and chemical properties of flour, as well as near infrared (NIR) spectra, is presented. The approach considers Multivariate Control Charts for both kinds of measurements, developed on flour batches employed in production. It can be adopted at the Millers laboratories, where rheological flours properties are routinely determined, to monitor flour quality; as well as, at the Bakeries plants, where NIR spectra of every flour batch entering the production can be acquired.Moreover, the variation of protein subunits in flour batches is discussed comparatively with flours properties and bread quality. Overall, flour batches leading to lousy performance can be individuated and they also show a non-optimal protein profile.This is of particular interest from the point of view of assessing flour workability and to rationalize it in terms of flour features. Finally, NIR potentiality allows considering on-line implementation in the control of incoming raw materials.
2011
- NEW TRACKING AND TRACING PERSPECTIVES FOR THE OENOLOGICAL CHAIN VALORISATION
[Relazione in Atti di Convegno]
Bertacchini, Lucia; Durante, Caterina; Donato, Lanati; Marchetti, Andrea; Dora, Marchi
abstract
The present work is part of a wide research project focused on the development of authenticity and geographical traceability models of wines, in particular Lambrusco wines, which are one of the main typical products of the Modena district. The analytical approach takes into account tools able to give information characterized by an high accuracy and precision as well as multivariate chemometrics techniques aimed to: i) plan a systematic and representative sampling (both for soils and food), ii) optimize the analytical methods used for the determination of the investigated parameters and iii) develop robust traceability models. In particular, in this study, an innovative approach based on the synergistic use of the experimental design technique, DoE, and principal component analysis, PCA, were used to plain a representative soil samples. Finally, the 87Sr/86Sr ratio has been monitored in a set of representative soils and grape-juices samples in order to verify and establish a link between the soils and the investigated wine based products focused on objective traceability indicator.
2011
- Optimization of a Dynamic Headspace – Thermal Desorption – Gas Chromatography/Mass Spectrometry procedure for the determination of furfurals in vinegars
[Articolo su rivista]
S., Manzini; Durante, Caterina; Baschieri, Carlo; Cocchi, Marina; Sighinolfi, Simona; S., Totaro; Marchetti, Andrea
abstract
The use of a Dynamic Headspace System (DHS) device combined with a Thermal Desorption Unit (TDU) interfaced to a Gas Chromatography/Mass Spectrometry (GC/MS) system is proposed for the determination of furfurals in oenological products. An experimental design protocol has been employed for the optimization of the instrumental settings concerning DHS and TDU extraction and desorption steps. It has been possible to individuate the following optimized conditions: incubation temperature 40 °C, purge volume 800 mL, dry volume 1500 mL, TDU hold time 5 min and incubation time 10 min. The performance of two different SPE sorbents, namely Tenax TA and Tenax GR used for the furfurals trapping, was investigated too. The developed DHS sampling procedure showed good reproducibility values with a RSD% lower than 10% for all the monitored species. The optimized experimental settings have been used to determine furfurals in several vinegar samples obtained by traditional procedure starting from cooked grape musts, i.e. in Aceto Balsamico Tradizionale di Modena (ABTM). In fact, the control of these species is extremely important for quality and safety issues.
2011
- Optimization of microwave assisted digestion procedure by means of chemometric tools
[Capitolo/Saggio]
Cocchi, Marina; Durante, Caterina; Marchetti, Andrea; LI VIGNI, Mario; Baschieri, Carlo; Bertacchini, Lucia; Sighinolfi, Simona; Tassi, Lorenzo; S., Totaro
abstract
The introduction of microwave (MW) heating devices inthe “chemical laboratory” represents one of the most important andrelevant application that contributes to speed up the “samplepreparation” step and, therefore, dramatically reduces the timeneeded for the analytical response. On the other hand, few andgeneric are the criteria developed to compare analytical dataobtained with conventional sample preparation approach withrespect to the MW one. In fact, when reference materials, RMs, arenot available, or not sufficiently representative of the real matrixunder investigation, it is often difficult to know when the sampledisgregation has come to completeness or if it is still possible tosave more time on the MW heating process. This contribute willdeal with the use of the more innovative Design of Experimentstools to the MW assisted digestion of organic rich matrices focusing on the potentialities of these experimental approaches when developing new disgregation analytical methods. The experimental approach concerns in finding the “optimum process conditions” in terms of solvent reaction mixture and recovery metal content.
2011
- Seeds of Horse Chestnut (Aesculus hippocastanum L.) and Their Possible Utilization for Human Consumption
[Capitolo/Saggio]
Foca, Giorgia; Ulrici, Alessandro; Cocchi, Marina; Durante, Caterina; LI VIGNI, Mario; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo
abstract
This chapter appraises the seeds of horse chestnuts (. Aesculus hippocastanum [AH]) and their derived products. Escin, the major bioactive principle in AH seeds, has shown satisfactory evidence of clinically significant activity in the treatment of chronic venous insufficiency, hemorrhoids, postoperative edema, and mammary induration. There is some evidence that various escin molecules, such as saponins and sapogenins, show beneficial effects when administered at the right concentration, exhibiting an ethanol absorption inhibitory effect and hypoglycemic activity in the oral glucose tolerance test in vivo. Horse chestnut extract has a higher antioxidant activity than vitamin E, showing one of the highest "active-oxygen" scavenging abilities compared to other natural products. β-Escin from AH extracts was also tested to evaluate the chemopreventive efficacy of its dietary intake on azoxymethane-induced colonic aberrant crypt foci. The main adverse effects of escins in humans are due to their hemolytic activity. Research efforts in this field are devoted to improving the selectivity for aberrant red corpuscles, promoting the β-escin fraction as a useful candidate agent for exploring new potential antileukemic drugs. Fresh or naturally desiccated seeds are usually treated by long leaching with water or wooden ashes to remove harshness and bitterness. These treatments cause a variation in the molecular structures of escin fractions, reducing the toxicity but maintaining their nutraceutical potential and anti-obesity effects. Alternatively, the slow roasting of nuts makes the escins harmless and the seeds edible. The claimed toxicity of these extracts makes them natural antibacterials, antimicrobials, antivirals, and antifungals, to some extent, that also act as environmentally biocompatible phytotherapeutics.
2009
- Near Infrared Spectroscopy and Multivariate Analysis methods for monitoring flour performance in an industrial bread-making process
[Articolo su rivista]
LI VIGNI, Mario; Durante, Caterina; Foca, Giorgia; Marchetti, Andrea; Ulrici, Alessandro; Cocchi, Marina
abstract
The present study is aimed at evaluating the possibility to predict bread specifications, for an industrial bread-making process, on the basis of the properties of flour employed in production. The flour delivered at the production plant, of which rheological and chemical properties were available, were analysed by means of Near Infrared Spectroscopy (NIRS). Based on the flour properties and NIR signals, multivariate control charts were constructed in order to detect flour batches leading to a bread with non-optimal behaviour. The results show that it is possible to distinguish flour batches leading to a product with a particularly negative performance, by modelling the properties commonly measured on flours and the acquired Near Infrared signals. In spite of the absence of monitoring of process variables, which could have offered a more sound basis for the interpretation, especially when false positives and negatives are detected, these results are of particular interest from the point of view of raw material evaluation in process monitoring. Also, the potentiality of Near Infrared Spectroscopy allows considering this approach for an on-line implementation in the control of incoming raw materials in this industrial process.
2009
- Study of protein content of wheat flour in relation to technological properties using chromatography, NIRS and chemometrics
[Relazione in Atti di Convegno]
Baschieri, Carlo; LI VIGNI, Mario; Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Ulrici, Alessandro
abstract
-
2008
- At-line control of an industrial bread-making process
[Abstract in Atti di Convegno]
LI VIGNI, Mario; Brettagna, B; Cocchi, Marina; DE MARCO, T; Foca, Giorgia; Marchetti, Andrea; Ulrici, Alessandro
abstract
-
2008
- Changes in the Chemical Composition of Reduced Cooked Musts During the Heating Process
[Articolo su rivista]
Cocchi, Marina; R., Consonni; Manzini, Simona; Sighinolfi, Simona; M., Grandi; Durante, Caterina; Marchetti, Andrea
abstract
Cooked must is the starting raw material in Aceto Balsamico Tradizionale di Modena (ABTM) production, and the cooking process is a crucial step to ensure quality and safety standards. In particular, the furfural content has to be strictly monitored. In this study, we followed, directly at the production plant, nine cooking processes, differing for grape type and process conditions in order to monitor the actual variability in cooked must reduction. 5-Hydroxymethylfurfural (5-HMF) and furfural contents were determined by high performance liquid chromatography (HPLC) technique and glucose, fructose, and tartaric and malic acids by gas chromatography (GC) technique. Furthermore, some bulk properties, such as the water content, refractive index, density, and total acidity, were also measured. The obtained results show that the product undergoes, in the worse operating conditions, remarkable degradation, leading to extremely high levels of furfurals (5-HMF and furfural), corre- sponding to a water content lower than 40%. On the basis of these results, a first draft of an optimal heating protocol may be suggested in order to guarantee the safety and quality of the final product.
2008
- Controllo di un processo industriale di panificazione mediante NIRS ed analisi multivariata
[Abstract in Atti di Convegno]
LI VIGNI, Mario; Brettagna, B; Cocchi, Marina; DE MARCO, T; Foca, Giorgia; Marchetti, Andrea; Ulrici, Alessandro; Quaglia, L.
abstract
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2008
- Modelling of Experimental Thermophysical Data by Mixing of a Ternary Solvent System, in Solution Chemistry
[Capitolo/Saggio]
Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Thermomechanic and thermodynamic properties of mixing solvents in the liquid state have proven a powerful tool in elucidating the specific interactions and structural features supporting the liquid structure in multicomponent nonelectrolytic solutions. Mass transport properties (density, viscosity), thermophysical properties (relative permittivity, refractive index), and related thermodynamics can deepen elucidate the solvent – solvent specific interactions and behavioural peculiarities of the complex real systems. In this paper, we will primarily deal with the experimental measurements and correlative studies both on temperature and composition, of the above mentioned properties (Y), working with a ternary solvent system containing 1,2-ethanediol (ED), 2-methoxyethanol (ME) and 1,2-dimethoxyethane (DME), at various temperatures in the range -10 £ t (°C) £ 80, and with different compositions covering the whole miscibility field of the selected species. These components are strictly parent species, all being 1,2-ethanedyil-derivatives (-CH2-CH2-), pertaining to the amphiphile class molecules, with different balancing degree of hydrophobic and hydrophilic properties. Furthermore, the excess properties (YE) and deviation functions (DY) are largely stressed and examined along the text in order to identify the presence of solvent – cosolvent adducts in these ternary mixtures.
2008
- Multivariate analysis of analytical signals to decipher relevant chemical information
[Capitolo/Saggio]
Ulrici, Alessandro; Cocchi, Marina; Durante, Caterina; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo
abstract
Two main elements have recently characterized the research in the analytical field: on one hand the huge development of instrumental analysis in the direction of hyphenated techniques and, on the other hand, the huge development and decreasing cost of computers together with the increased capacity of computational tools. Moreover, new issues are presented to the analytical researcher by new regulations that impose to demonstrate that the whole process is under control, e.g. in the industrial/productive context, or in the life science context by the emerging need of systems biology. Thus, the role of chemometrics is more and more increasing and the toolbox of chemometrics-like methods has been progressively enriched.In particular, deciphering signal-fingerprinting of complex matrix samples requires a deeper consideration on the nature of signals feature, and it has to be taken into account that the information pertinent to the problem is mixed with many uninformative sources of variations that may affect part or the whole signal domain. These issues from the data analysis point of view are reflected in a greater complexity of the preprocessing/pretreatment and variable selection steps.The main focus of this chapter will be on feature selection methodology; after a concise review of the main recently proposed feature selection methods, the specific case of feature selection in the wavelet (WT) domain will then be considered. In particular, it will deal with illustration of our recent developed tools for WT-feature selection in regression and classification tasks. The discussion of different applications will be the core of the work, to illustrate the effectiveness of the integration of both basic (simple) and more advanced methodologies together, with a complete strategy embracing data exploration, modelling, data display-interpretation and validation.
2008
- Three-way principal component analysis of the volatile fraction by HS-SPME/GC of aceto balsamico tradizionale of modena
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; Grandi, Margherita; Manzini, Daniela; Marchetti, A.
abstract
The present research is aimed at monitoring the evolution of the volatile organic compounds of different samples of Aceto Balsamico Tradizionale of Modena (ABTM) during ageing. The flavouring compounds, headspace fraction, of the vinegars of fourbatterie were sampled by Solid Phase Micro Extraction technique (SPME), and successively analysed by gas chromatography. Obtaining a data set characterized by different sources ofvariability such as, different producers, samples of different age and chromatographic profile. The gas chromatographic signals were processed by a three-way data analysis method (Tucker3), which allows an easy visualisation of the data by furnishing a distinct set of graphs for each source of variability.The obtained results indicate that the samples can be separated according to their age highlighting the chemical constituents, which play a major role for their differentiation. The present study represents an example of how the application of Tucker3 models, on Gas Chromatographic signals may help to follow the transformation processes of food products.
2007
- Caratterizzazione del Nocino tipico emiliano mediante indagini chimico-fisiche ed analisi chemiometriche
[Relazione in Atti di Convegno]
Foca, Giorgia; Franchini, Giancarlo; Grandi, Margherita; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
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2007
- Characterization and discrimination of different aged 'Aceto Balsamico Tradizionale di Modena' products by Head Space mass spectrometry and Chemometrics
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; Marchetti, Andrea; C., Armanino; M., Casale
abstract
This work can be seen as an attempt to develop an analytical procedure in the context of quality control and authenticity assessment of typical food. To this aim, head-space mass spectrometry (HS-MS) coupled with multivariate data analysis, is proposed as a fast technique for furnishing a clear visualization and a suitable interpretation of the ageing process of ‘Aceto Balsamico Tradizionale di Modena’ (ABTM) and, for classifying products of different age. Considering the complexity of this food matrix, due to its traditional making procedure, the obtained instrumental data have first been analysed by parallel factor analysis (PARAFAC), an extension of principal component analysis to higher order arrays, in order to visualise the ‘natural’ grouping of vinegar samples and to inspect producers similarity/dissimilarity. On the basis of the PARAFAC results a reasonable class partition with respect to ageing was accomplished and both linear discriminant analysis (LDA) and soft independent modelling of class analogy (SIMCA) were applied as classification tools. Furthermore, it has been shown that discrimination on age basis can be improved by using feature selection in the wavelet domain through WPTER algorithm.
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
- Determinazione di acidi e zuccheri presenti negli impasti per la produzione industriale di pane a diversi stadi della lavorazione
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; LI VIGNI, Mario; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
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2007
- Evaluation of the oxidation state and metal concentrationin the adipose tissue of Parma ham
[Articolo su rivista]
G., Ferrari; P., Lambertini; D., Manzini; Marchetti, Andrea; S., Sighinolfi; G., DELLA CASA
abstract
The effect of different dietary fat supplements: A, no added fat; B, 3% added lard and C, 3% added partially hydrogenated lard (PHL),were evaluated in dry cured Parma ham fat by determination of the lipid oxidation indices, R1 and R2, on a total of 30 Italian Landrace· Italian Large White pigs. Furthermore, correlations between lipid oxidation and calcium, magnesium, iron, zinc, copper andnickel concentrations, determined in Parma ham fat, was also investigated. Results highlighted a correlation between the oxidative stateof Parma ham fat and the pigs’ diet; in particular the addition of 3% PHL led to a more stable depot fat towards lipid oxidation comparedto the addition of lard. Finally, Parma ham fat from treatment C showed higher concentrations of Ca (p < 0.01) and Mg (p < 0.05)compared to those from control, A, and treatment B groups. On the contrary, no significant differences were found for Fe, Zn, Cu andNi.
2007
- Monitoraggio multivariato di un processo industriale di panificazione
[Relazione in Atti di Convegno]
Belloni, P; Brettagna, B; Cocchi, Marina; DE MARCO, T; Foca, Giorgia; LI VIGNI, Mario; Marchetti, Andrea; Ulrici, Alessandro
abstract
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2007
- Monitoring an industrial bread making process by means of Near Infrared Spectroscopy and chemometric methods
[Relazione in Atti di Convegno]
P., Belloni; B., Brettagna; Cocchi, Marina; T., De Marco; Durante, Caterina; Foca, Giorgia; LI VIGNI, Mario; Marchetti, Andrea; Ulrici, Alessandro
abstract
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2007
- Monitoring of the leavening process in industrial bread making
[Relazione in Atti di Convegno]
Belloni, P; Brettagna, B; Cocchi, Marina; DE MARCO, T; Foca, Giorgia; LI VIGNI, Mario; Marchetti, Andrea; Ulrici, Alessandro
abstract
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2007
- Study of the monosaccharides and furfurals evolution during the preparation of cooked grape musts for Aceto Balsamico Tradizionale production
[Articolo su rivista]
Cocchi, Marina; G., Ferrari; Manzini, Daniela; Marchetti, Andrea; Sighinolfi, Simona
abstract
Cooked must is the starting raw material used to produce Aceto Balsamico Tradizionale (ABT). It is obtained from grape musts that are condensed by a gentle simmering in uncovered pans over an open fire. Concentrations of fructose, glucose, furfural and 5-Hydroxymethylfurfural (HMF) during must preparation were evaluated as quality indicator of the final product. High pressure liquid chromatography (HPLC) technique was used for the determination of the analytes content in cooked musts sampled at different time during their preparation. Two varieties of grapes (Trebbiano Montanaro and Salamino), and different cooking apparatus were tested by using vats with different surface/volume ratio. The concentrations of the analytical species were found to be dependent on both the kind of grape and the cooking technology. Sugars concentration increases during cooking following almost a linear trend; on the contrary, furfural compounds, produced by monosaccharides degradation, significantly increase with an exponential trend only in the final step of the process. The analytical method gives good recovery values for all the investigated species, ranging from 91% to 104 %. (c) 2006 Elsevier Ltd. All rights reserved.
2006
- Analysis of Sensory data of Aceto Balsamico Tradizionale di Modena (ABTM) of different ageing by application of PARAFAC models.
[Articolo su rivista]
Cocchi, Marina; R., Bro; Durante, Caterina; Manzini, Daniela; Marchetti, Andrea; F., Saccani; Sighinolfi, Simona; Ulrici, Alessandro
abstract
Aceto Balsamico Tradizionale di Modena is a typical Italian food product of protected denomination of origin, obtained by alco- holic fermentation and acetic bio-oxidation of cooked musts, and it is aged for at least 12 years in series of wooden casks. The prod- uct suitable for marketing is qualified by sensory examination on the whole of 13 sensory parameters. In this study, a series of six casks for each of seven different producers have been investigated by an expert Panel of eight judges, aiming at (i) assessing the degree of variability of the different sensorial attributes with samples ageing, and (ii) evaluating the sim- ilarity/dissimilarity among the various parameters together with the degree of agreement of the panellists. Given the three-way nature of the data (samples · panellists · sensory attributes) the PARAFAC method has been used, and a satisfactory model was obtained, highlighting the efficacy of three-way analysis in dealing with the different sources of data variabil- ity, extracting the relevant information and displaying it in a simple and interpretable manner.
2006
- Application of N-PLS to gas chromatographic and sensory data of traditional balsamic vinegars of modena
[Articolo su rivista]
Durante, Caterina; Cocchi, Marina; M., Grandi; Marchetti, Andrea; R., Bro
abstract
The application of multi-way models in food analysis as in many other research fields is rapidly increasing, above all because it can significantly help to improve visualization and interpretation of complex multivariate data characterized by different sources of variability. Furthermore, in food authentication tasks a fingerprinting strategy is frequently applied which requires the direct analysis of complex instrumental data, often obtained by hyphenated analytical techniques, which lead to multi-way data. In this work, the main features and advantages of multi-way regression are presented through the study of the evolution of the sensory and compositional profile during the ageing process of Aceto Balsamico Tradizionale di Modena (ABTM), a typical Italian food product, which represents a very interesting benchmark for testing new analytical methodologies due to its long ageing process and the peculiarity of the traditional making procedure. A series of 6 casks for each of 6 different producers has been characterized through sensory and instrumental analysis of the volatile fraction by head space-solid phase micro extraction/gas chromatography (HS-SPME/GC). The N-PLS method has been used as regression method since many sources of variability have to be taken into account, e.g. different cask series, different samples ageing, different panelists, etc. The validity of this choice is evaluated by comparing with results obtained from unfold-PLS method. Satisfactory regression models were obtained, highlighting the efficiency of the three-way model, which was shown to be more robust and interpretable.
2006
- Controllo at-line di impasti per la produzione industriale di pane mediante tecniche analitiche e chemiometriche
[Relazione in Atti di Convegno]
Foca, Giorgia; Ulrici, Alessandro; Cocchi, Marina; Marchetti, Andrea; LI VIGNI, Mario
abstract
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2006
- Durum wheat adulteration detection by NIR spectroscopy multivariate calibration
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
In the present work, we explored the possibility of using near-infrared spectroscopy in order to quantify the degree of adulteration of durum wheat flour with common bread wheat flour. The multivariate calibration techniques adopted to this aim were PLS and a wavelet-based calibration algorithm, recently developed by some of us, called WILMA. Both techniques provided satisfactory results, the percentage of adulterant present in the samples being quantified with an uncertainty lower than that associated to the Italian official method. In particular the WILMA algorithm, by performing feature selection, allowed the signal pretreatment to be avoided and obtaining more parsimonious models.
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
- Monitoraggio at-line del processo di lievitazione di impasti per la produzione industriale di pane
[Relazione in Atti di Convegno]
Ulrici, Alessandro; Cocchi, Marina; Marchetti, Andrea; Foca, Giorgia; Durante, Caterina; DE MARCO, T; Brettagna, B; Belloni, P.
abstract
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2006
- Simultaneous determination of sugars and organic acids in aged vinegars and chemometric data analysis
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; M., Grandi; P., Lambertini; Manzini, Daniela; Marchetti, Andrea
abstract
Aceto Balsamico Tradizionale of Modena (ABTM) is a typical product (PDO denomination) of the province of Modena produced by cooked grape must which undergoes a long ageing period (at least 12 years) in series of wooden casks (batterie). The study of the transformations of this product during ageing is extremely relevant in order to control the authenticity of ABTM towards succedaneous products and mislabelling of age. This paper presents the results of the investigation of sugars and fixed organic acids in ABTM samples of different ages, coming from different batterie. The analytes were simultaneously determined by a gas chromatographic method optimised for this peculiar matrix. The method shows good separation and resolution of the investigated chemical species and allows their determination in the concentration ranges reported in brackets: malic (7.6-15.5 g kg(-1)), tartaric (4.0-9.7 g kg(-1)), citric (0.6-1.5 g kg(-1)) and succinic (0.36-0.62 g kg(-1)) acid and glucose (153-294g kg(-1)), fructose (131-279g kg(-1)), xylose (011-0.39g kg(-1)), ribose (0.078-0.429g kg(-1)), rhamnose (0.061-0.195g kg(-1)), galactose (0.136-0.388g kg(-1)), mannose (0.41-1.46g kg(-1)), arabinose (0.33-1.00g kg(-1)) and sucrose (0.46-6.84g kg(-1)), with mean associated errors ranging from 5 to 19% depending on the analytes. Moreover, the recovery values are always satisfactory, being close to one for most of the analytes. Furthermore, in order to assess the degree of variability of the different analytes content with vinegar ageing and the similarity/dissimilarity among series of casks a three-way data analysis method (Tucker3) is proposed. The chemometric technique applied on the data set shows differences between the samples on the bases of their different ageing period, and between the batterie, which traditionally have an own peculiar production procedure.
2006
- Study of the dependence on temperature and composition of the volumic properties of ethane-1,2-diol+2-methoxyethanol+1,2-dimethoxyethane plus water solvent system and graphical representation in the quaternary domain
[Articolo su rivista]
Ulrici, Alessandro; Cocchi, Marina; Foca, Giorgia; M., Manfredini; Marchetti, Andrea; D., Manzini; Tassi, Lorenzo; S., Sighinolfi
abstract
In this paper, the temperature and composition dependencies of the volumetric behavior are studied for the ethane-1,2-diol + 2-methoxyethanol + 1,2-dimethoxyethane + water quaternary system. Density data were collected at different temperatures ranging from -10 to 80 degrees C and at atmospheric pressure over the whole composition range, 0 :5 x(i)(i = 1, 2, 3,4) <= 1. Moreover, we also made use of the results on the six binary (ij) and four ternary (kij) subsystems studied previously. The excess molar volume (V-E) data have been fitted to an equation derived from the well-known Redlich-Kister equation and some interesting correlations were found. Furthermore, in order to represent in an effective way the behavior of the V-E = V-E(x(i)) function (and of the derived partial molar quantities) in the quaternary domain, a new algorithm has been developed, which gives 3D plots where the dependent function is depicted by means of '' colored slices '' of the tetrahedron corresponding to the investigated composition quaternary domain.
2006
- Thermal stability and chemical durability of PVC-based biomedical devices
[Articolo su rivista]
Manfredini, M; Bodecchi, Lidia Maria; Marchetti, Andrea
abstract
Poly(vinyl chloride) (PVC)-based blood circuits for extracorporeal hemodialysis were investigated for the assessment of their thermal stability as well as their chemical durability towards ionizing radiation sterilization and environmental conditions of storage and transportation. Thermal degradation was monitored by measuring the amount of hydrochloric acid (HCl) evolved as a function of different thermal stresses. HCl was extracted from the internal lumen of the blood circuits, and then quantitatively evaluated under the corresponding form of chloride ions by chromatographic technique (HPLC-IC). Behavior of PVC heat stabilizers was evaluated as well, determining also the concentration of calcium and zinc released by the investigated materials, by flame atomic absorption spectroscopy (FAAS) technique. Electron beam irradiation revealed an impact on blood tubing higher than that of environmental storage conditions. Nevertheless, real operative cases of sterilization and storage conditions turned out to be quite safe, and all blood circuits displayed good performances in terms of thermal stability. (c) 2006 Wiley Periodicals, Inc.
2005
- Application of IR spectrometry and multivariate quality control methods in PVC manufacturing
[Relazione in Atti di Convegno]
Bodecchi, L. M.; Ferrari, Giorgia; Manzini, D.; Manfredini, M.; Marchetti, Andrea
abstract
Application of IR Spectrometry and Multivariate Quality Control Methods in PVC Manufacturing.
2005
- Application of NIR spectroscopy and Principal Component Analysis on the monitoring of PVC industrial process for biomedical application
[Relazione in Atti di Convegno]
Bodecchi, Lidia Maria; Cocchi, M.; Manfredini, Matteo; Marchetti, Andrea
abstract
Application of NIR spectroscopy and Principal Component Analysis on the monitoring of PVC industrial process for biomedical application.
2005
- Application of infrared spectroscopy and multivariate quality-control methods in PVC manufacturing
[Articolo su rivista]
M., Manfredini; Cocchi, Marina; Lm, Bodecchi; G., Ferrari; Marchetti, Andrea; M., Malagoli; F., Galavotti
abstract
This work aims at exploring the potentiality of the Fourier transform IR spectroscopy (FTIR) to study the effects that can be generated on plastic materials based on poly(vinyl chloride) (PVC) used for extra-corporal medical disposables, after industrial processes such as extrusion, sterilization and conservation. In particular, FTIR equipped with a single attenuated total reflection accessory (ATR) mounted on an infrared microscope (Mic-IR) has been used. At the same time, this paper proposes a quality-control method for semi-finished blood circuits´ components, based on the chemometric evaluation of surface-selective spectroscopic signals, i.e. Mic-IR/ATR spectra. Results suggest that IR spectroscopic technique coupled with a multivariate approach might represent a simple and powerful method for quality control of industrial processes.
2005
- Application of multy-way analysis to the study of food products
[Relazione in Atti di Convegno]
Cocchi, Marina; Durante, Caterina; Grandi, Margherita; Manzini, Daniela; Marchetti, Andrea; BRO JORGENSEN, Rasmus
abstract
Application of Multy-Way Analysis to the Study of Food Products.
2005
- Determination of metal concentration in fat supplements for swine nutrition by atomic absorption spectroscopy
[Articolo su rivista]
Cocchi, Marina; V., Faeti; M., Manfredini; Manzini, Daniela; Marchetti, Andrea; Sighinolfi, Simona
abstract
The presence of some essential and toxic metals in fat supplements for swine diet was investigated. Collected samples represented a relevant production of the Italian industry. In particular, some samples were enriched with antioxidants or waste cooking oils. The method for the determination of Ca, Cu, Cd, Fe, Mg, Mn, Ni, Pb, and Zn in fat samples was developed by means of a certified reference material (CRM 186) and a representative fatty sample (RFS). All samples were digested in closed vessels in a microwave oven and then analyzed by flame atomic absorption or graphite furnace atomic absorption spectrometry. The entire analytical method provided a satisfactory repeatability and reproducibility confirmed by agreement between the experimental recovery data obtained for the CRM 186 sample and, with the method of standard additions, for the RFS material. The samples generally showed a small amount of metals compared with the recommended daily intake for the essential elements. On the other hand, some samples contained a significant concentration, from an analytical point of view, of Cd, Ni, and Pb. Principal component analysis (PCA) was applied to inspect the experimental data obtained from samples analysis. Basically no differences were detected in terms of metal concentration among the fat supplements analyzed.
2005
- Use of multivariate analysis of MIR spectra to study bread staling
[Articolo su rivista]
Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Different kinds of bread, stored at constant temperature and at controlled humidity conditions for a week since their manufacturing date, were analysed by Attenuated Total Reflectance-Fourier Transform InfraRed (ATR-FTIR) spectroscopy. The collected spectra were processed by Principal Component Analysis (PCA), in order to evaluate the changes occurring during bread ageing. For the sake of comparison, the 1060-950 cm(-1) spectral window has been also investigated by curve-fitting methods. It was observed that the first PC increases monotonically with ageing of samples. Furthermore, the more influential variables on PCl correspond to spectral regions where are located stretching and bending bands, which are mainly attributed to typical starch bonds vibrations.
2004
- A chemometric approach to the comparison of different sample treatments for metals determination by atomic absorption spectroscopy in aceto balsamico tradizionale di modena
[Articolo su rivista]
Cocchi, Marina; Franchini, Giancarlo; D., Manzini; Marchetti, Andrea; M., Manfredini; Ulrici, Alessandro
abstract
A comparison of different digestion procedures has been carried out for the analysis of metal concentration in samples of vinegars and Aceto Balsamico Tradizionale of Modena (ABTM) coming from an unique barrel set. In particular, classical wet, dry ashing, and closed vessel microwave digestion procedure have been utilized and compared for each investigated species. In a few cases, direct metal determination on ABTM (without treatment procedure) is proposed as possible alternative to sample manipulation. Flame atomic absorption spectrometry was used for the quantification of iron and zinc, while graphite furnace atomic absorption spectrometry was used for all the other elements (i.e., chromium, manganese, cobalt, nickel, copper, cadmium, and lead). The comparison among the different sample treatments was carried out by the use of statistical and chemometric tools. In particular, principal component analysis and ANOVA approaches were used to discriminate between the diverse analytical methods. Furthermore, for all the dissolving techniques, the analytical metal recovery was always evaluated by the application of the recovery function on the same sample matrix. In general, the recoveries were fairly good, ranging from 90 to 103%, except for Cd and Pb with dry ashing, which showed recovery values close to 55% and 67%, respectively. As regards the metals concentration of the investigated samples, the experimental data reveal for some species the presence of concentration slightly over the legal limit fixed for wine and wine vinegar.
2004
- A study of the dielectric behavior and the liquid structure of a ternary solvent system
[Articolo su rivista]
Cocchi, Marina; Franchini, Giancarlo; Marchetti, Andrea; Pigani, Laura; Seeber, Renato; Tassi, Lorenzo; Ulrici, Alessandro; Zanardi, Chiara; Zannini, Paolo
abstract
The static dielectric constant of the {DMF(1) + ME(2) + DME(3)} ternary mixtures was measured as a function of temperature (25 less than or equal to t/degreesC less than or equal to 80) and composition, over the whole mole fraction range 0 less than or equal to x(1),x(2),x(3) less than or equal to 1. The experimental values were processed by an empirical equation accounting for the dependence epsilon = epsilon(T, phi(i)), where phi(i) is the volume fraction of the components. A comparison between calculated and experimental data shows that this fitting relationship can be effectively employed to predict epsilon values in correspondence to experimental data gaps. Starting from the experimental measurements, some derived quantities such as molar polarisation (P), and excess counterpart (P-E) were obtained. Both the excess properties, epsilon(E) and P-E, take values partly positive and partly negative under all experimental conditions. The values of the excess quantities are indicative of the presence of specific interactions among different components in the mixtures.
2004
- Analysis of the temperature and composition dependence of viscosimetric properties of 2-butanone+2-butanol solvent mixtures
[Articolo su rivista]
S., Faranda; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro; Zucchi, Claudia
abstract
Kinematic viscosities were measured for 2-butanone + 2-butanol binary liquid mixtures with a capillary Ubbelohde routine viscometer in the temperature range from 273.15 to 353.15 K at atmospheric pressure, and covering the whole miscibility field (0 less than or equal to x(i) less than or equal to 1). Experimental data have been correlated by means of different empirical or semiempirical relationships, such as nu = nu(T), nu = nu(x(i)), and nu = nu(T, x(i)). Viscosity deviations, Deltanu, from ideal behavior are negative at all experimental conditions, confirming that structure breaking effects prevail in the liquids. Furthermore, the thermodynamics of viscous flow and excess Gibbs energy of activation of viscous flow, G*(E), have been calculated. As an alternative and complementary approach to such investigations, the fluidity (phi) of this binary system has been analyzed by the modified-Batschinski theory. The results are discussed in terms of the specific molecular interactions between the mixture components.
2004
- Application of NIR spectroscopy multivariate calibration to the quantification of durum wheat semolina adulteration with bread wheat flour
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
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2004
- Application of a wavelet-based algorithm on HS-SPME/GC signals for the classification of balsamic vinegars
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; Foca, Giorgia; Manzini, Daniela; Marchetti, Andrea; Ulrici, Alessandro
abstract
A novel feature selection and classification algorithm (WPTER) based on the wavelet packet transform has been applied to the discrimination of balsamic vinegars, namely the typical made Aceto Balsamico Tradizionale di Modena, which gained the PDO denomination on the year 2000, from the industrial made Aceto Balsamico of the Modena district. All the samples have been characterized on the basis of the gas chromatographic (GC) profiles of the headspace (HS) volatile fraction, sampled by solid phase microextraction (SPME). Good discrimination between the two categories has been obtained both for the calibration and for the test set samples. GC-MS analysis allowed the identification of the peaks lying in the chromatographic regions selected by the algorithm, giving useful suggestions about the compounds which may be worth of further investigation in order to rationalize the chemical transformation occurring during the traditional making procedure. The proposed methodology seems very promising in authentication tasks, coupling some of the advantages of blind analysis with the possibility of acquiring chemical information, and giving, at the same time, very parsimonious multivariate classification models, which can be particularly suitable for data storage and handling.
2004
- Applicazione della calibrazione multivariata su spettri NIR per la quantificazione dell’adulterazione di semola di grano duro con farina di grano tenero
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
-
2004
- Caratterizzazione chimico-fisica di amidi di varia origine
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; Franchini, Giancarlo; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo; Ulrici, Alessandro
abstract
-
2004
- Chemical durability of PVC based biomedical devices
[Relazione in Atti di Convegno]
Bodecchi, L. M.; Cocchi, M.; Marchetti, Andrea; Manfredini, M.
abstract
Il ruolo delle variabili temperatura e tempo è stato investigato relativamente alle proprietà funzionali di dispositivi disposables per uso biomedicale
2004
- Classification of cereal flours by chemometric analysis of MIR spectra
[Articolo su rivista]
Cocchi, Marina; Foca, Giorgia; M., Lucisano; Marchetti, Andrea; Ma, Pagani; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Different kinds of cereal flours submitted to various technological treatments were classified on the basis of their mid-infrared spectra by pattern recognition techniques. Classification in the wavelet domain was achieved by using the wavelet packet transform for efficient pattern recognition (WPTER) algorithm, which allowed singling out the most discriminant spectral regions. Principal component analysis (PCA) on the selected features showed an effective clustering of the analyzed flours. Satisfactory classification models were obtained both on training and test samples. Furthermore, mixtures of varying composition of the studied flours were distributed in the PCA space according to their composition.
2004
- Density measurements of the binary mixtures of 2-butanone and 2-butanol at temperatures from –10 to 80 °C
[Articolo su rivista]
S., Faranda; Foca, Giorgia; Marchetti, Andrea; Palyi, Gyula; Tassi, Lorenzo; Zucchi, Claudia
abstract
Densities of methyl-ethyl-ketone + 2-butanol were measured at temperatures between -10 and 80 degreesC, working with the pure species and nine binary mixtures. At each experimental condition, the data were correlated by means of some empirical equations and according to well-established literature models. The estimated excess molar volumes (and some related quantities) were also evaluated by applying the Redlich-Kister equation. The results related to specific intermolecular interactions have been interpreted in terms of structural and geometrical effects.
2004
- Dielectric properties in ternary mixtures of ethane-1,2-diol+1,2-dimethoxyethane + water
[Articolo su rivista]
Foca, Giorgia; Manfredini, Matteo; Manzini, Daniela; Marchetti, Andrea; Pigani, Laura; Sighinolfi, Simona; Tassi, Lorenzo; Ulrici, Alessandro
abstract
The static dielectric constant (epsilon) of ethane-1,2-diol + 1,2-dimethoxyethane + water ternary mixtures was measured as a function of temperature (263.15 less than or equal to T (K) less than or equal to 353.15) and composition, over the complete mole fraction range 0 less than or equal to x(1), x(2), x(3) less than or equal to 1. The experimental values were analyzed by empirical relationships that accounted for the dependence epsilon = epsilon(T) and Y = Y(x(i)). A comparison between calculated and experimental data shows that these fitting relationships can be reliably used to predict epsilon values, along with other related properties, in areas of experimental data gaps. Starting from the experimental measurements, some derived quantities such as molar orientational polarization (P), dipolar interaction free energy (Fmu) and the relevant thermodynamic excess mixing properties (F-mu(E), (F) over bar (E)(mu,i)), were obtained. The values of the excess quantities are indicative of the presence of specific interactions between different components in the mixtures. A discussion of data in terms of the Kirkwood theory also provides information on the short-range intermolecular interactions, suggesting the formation of stable two-component adducts rather than of more complex moieties involving all three molecular species.
2004
- Stabilità termica di dispositivi biomedicali a base PVC
[Relazione in Atti di Convegno]
Bodecchi, L. M.; Cocchi, M.; Ferrari, G.; Manfredini, M.; Marchetti, Andrea
abstract
Stabilità Termica di Dispositivi Biomedicali a Base PVC.
2004
- Thermal Stability and Chemical Durability of PVC-Based Biomedical Devices
[Relazione in Atti di Convegno]
Bodecchi, M.; Cocchi, M.; Manfredini, M.; Marchetti, Andrea
abstract
The role of Analytical Chemistry in the Protection of the Citizen
2004
- Utilizzo del rapporto isotopico Sr87/Sr86 per lo sviluppo di modelli di traciabilità geografica di prodotti alimentari
[Relazione in Atti di Convegno]
Cocchi, Marina; Ferrari, Giorgia; Hoogewerff, J. A.; Manzini, Daniela; Marchetti, Andrea; Sighinolfi, Simona
abstract
Molti paesi europei vantano una notevole tradizione eno-gastronomica, che comprende numerose produzioni di alimenti tipici regionali di alto valore commerciale. Il consumo di tali prodotti si è diffuso largamente negli ultimi anni, e ciò ha indotto l’unione europea a tutelare tali alimenti tramite l’introduzione delle denominazioni di qualità, ossia Specialità Territoriale Garantita” (STG), “Indicazione Geografica Protetta” (IGP) e “Denominazione di Origine Protetta” (DOP).
La diffusione di alimenti tipici regionali ha incrementato notevolmente l’interesse verso lo sviluppo di metodi di tracciabilità, intesa come processo che segue l’alimento durante tutte le fasi della produzione, ossia come un insieme di informazioni sull’origine delle materie prime, sul luogo di produzione e sulle tecniche di produzione che portano all’ottenimento dell’alimento.
Finora la tutela dei prodotti tipici è stata legata, essenzialmente, ad una tracciabilità di tipo cartaceo ma, per individuare imitazioni o frodi legate a prodotti ottenuti in zone diverse da quelle di tutela, sta nascendo la necessità di una tracciabilità “oggettiva” basata, cioè, su criteri oggettivi che fanno riferimento a misure scientifiche .
L’impiego del rapporto isotopico di elementi stabili, unitamente alla concentrazione di metalli ed elementi in tracce può essere usata con successo per l’individuazione dell’origine geografica di un alimento, in quanto questi dati tendono a rimanere maggiormente costanti rispetto a numerosi composti organici che possono essere analogamente utilizzati per lo sviluppo di metodi di tracciabilità.
Tra i prodotti con denominazione DOP si inserisce l’Aceto Balsamico Tradizionale di Modena (ABTM) che rappresenta, probabilmente, uno degli alimenti tipici più conosciuti ed apprezzati dell’universo gastronomico mondiale.
La produzione di questo condimento di antica origine, derivante da mosti cotti di uve selezionate tipiche della provincia di Modena, avviene in botticelle di differenti essenze legnose e di diversa capacità, per fermentazione alcolica ed acetica seguita da una lunga maturazione in cui si verificano processi naturali di invecchiamento.
Dato il lungo periodo di invecchiamento e le peculiarità del processo produttivo, l’ABTM rappresenta una matrice molto interessante da un punto di vista scientifico e può essere considerato un “banco di prova” per lo sviluppo di un modello di tracciabilità.
In questo lavoro sono presentati i risultati di un primo studio pilota volto all’elaborazione di un sistema di tracciabilità per l’ABTM, mediante la determinazione del rapporto isotopico 87Sr/86Sr e della concentrazione degli elementi Ca, Mg, Sr, Cu, Cd, Zn, Fe, Pb.
Per la presente ricerca sono stati individuati alcuni produttori di ABTM, variamente dislocati nella provincia di Modena, i quali rincalzano le botti con mosto proveniente da uve di loro stessa coltivazione e conducono da tempo le batterie selezionate con mosto prodotto nelle loro aziende.
Presso tali produttori, sono state campionate le terre del vigneto, le acque eventualmente usate per l’irrigazione, i mosti cotti e gli aceti invecchiati.
Le tecniche MC-ICP/MS (multi collector ICP/MS), FAAS e GFAAS sono state usate per la misura del rapporto isotopico dello stronzio e per la determinazione della concentrazione totale dei metalli, rispettivamente. I dati ottenuti sono stati successivamente elaborati con tecniche di analisi chemiometrica.
I risultati ottenuti sono estremamente interessanti e promettenti, soprattutto per quanto concerne la possibilità di correlare le caratteristiche delle materie prime (mosti) con la composizione dei terreni di provenienza.
Le misure del rapporto isotopico 87Sr/86Sr hanno evidenziato, infatti, una relazione significativa tra mosti e terreni, correlabile alle diverse zone geologiche che si possono identificare nel territorio modenese.
Questi ri
2003
- Applicazione dell’Algoritmo WPTER per la Classificazione di Spettri MIR di Farine Provenienti da Diversi Careali
[Relazione in Atti di Convegno]
Cocchi, M.; Foca, G.; Marchetti, Andrea; Sighinolfi, S.; Tassi, L.; Ulrici, A.
abstract
l’Algoritmo WPTER è stato utilizzato per la Classificazione di prodotti da forno ottenuti impiegando cereali diversi mediante spettri MIR i
2003
- Applicazione dell’algoritmo WPTER per la classificazione di spettri MIR di farine provenienti da diversi cereali
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo; Ulrici, Alessandro
abstract
-
2003
- Characterization of “Aceto Balsamico Tradizionale di Modena” Ageing Process by Application of a Wavelet Based Algorithm on HS-SPME/GC Signals
[Relazione in Atti di Convegno]
Cocchi, Marina; Durante, Caterina; Manzini, Daniela; Marchetti, Andrea
abstract
The aceto balsamico tradizionale di Modena received the PDO certification from the EU two years ago.
2003
- Degradation of plasticized PVC for biomedical disposable device under soft x-ray irradiation
[Articolo su rivista]
D., Atzei; M., Manfredini; Marchetti, Andrea; B., Elsener; Rossi, Aldo
abstract
Plasticized poly(vinyl chloride) (PVC) used for biomedical disposable devices was studied in the non-sterilized state after different exposure times to soft x-ray irradiation in a commercial photoelectron spectrometer (Al Kalpha, 15 kV/300 W; Mg Ka, 12 kV/240 W) by XPS surface analysis. The detailed spectra of C1s, Cl 2p and O1s have been recorded and processed. Irradiation with soft x-rays induces a clear decrease of the total Cl 2p intensity, an increase of total C is intensity and a doubling of the O1s intensity after 45 min of irradiation with Al Ka (300 W). Irradiation with Mg Kalpha (240 W) is slightly less damaging. These results can be interpreted with the classical PVC degradation model, e.g. bond cleavage with the formation of HCl gas, although the Cl 2p high-resolution spectra reveal the formation of an additional side-product, probably CaCl2. For further studies of plasticized PVC using XPS surface analysis it can be concluded that a complete analysis of a polymer sample should not take >10 min of x-ray exposure in order to avoid notable polymer degradation. Copyright
2003
- Density and volume properties of the 2-chloroethanol+2-methoxyethanol+1,2-dimethoxyethane ternary solvent system at different temperatures
[Articolo su rivista]
Ferrari, Giorgia; Foca, Giorgia; M., Manfredini; Manzini, Daniela; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
The density of the 2-chloroethanol (CE) + 2-methoxyethanol (ME) + 1,2-dimethoxyethane (DME) ternary mixtures has been measured at different temperatures ranging from -10 to 80degreesC, and over the entire composition range. The experimental data have been used to check the validity of some relationships accounting for the dependence of the density on temperature and composition domains. Starting from the primary data, some derived quantities, such as excess molar volumes V-E, partial molar volumes (V) over bar (i) and partial excess molar volumes (V) over bar (E)(i), have been obtained. In these mixtures, V-E is always positive for the [CE(1) + ME(2)] binaries, while it is generally negative at all other experimental conditions, showing the greatest deviations along the binary axes corresponding to the binary subsystems in the sequence [CE(1) + DME(2)] < [CE(1) + ME(2)] < [ME(1) + DME(2)]. The results are compared and discussed to in terms of changes in molecular association and structural effects in these solvent systems.
2003
- Influence of Different Plasticizer Additives and Sterilization Techniques on the Surface Properties of PVC-Based Biomedical Disposable Devices
[Relazione in Atti di Convegno]
Atzei, D.; Manfredini, Matteo; Marchetti, Andrea; Elsener, B.; Rossi, A.
abstract
oral presentation
2003
- Radiation-induced migration of additives in PVC-based biomedical disposable devices Part 2. Surface analysis by XPS
[Articolo su rivista]
D., Atzei; B., Elsener; M., Manfredini; Marchetti, Andrea; M., Malagoli; F., Galavotti; Rossi, Antonio
abstract
Extruded parts of non-sterilized and P-irradiated (25 and 50 kGy) plasticized poly(vinyl chloride) (PVC) used for disposable medical devices have been studied to investigate the effect of sterilization on surface chemical composition. The polymer surfaces were analysed using angle-resolved x-ray photoelectron spectroscopy. The inner surface of the blood tubing lines showed a fairly smooth surface both before and after sterilization, so a laterally homogeneous surface can be assumed for XPS analysis. The XPS survey spectra exhibited no signals besides carbon, chlorine, oxygen and calcium. Detailed analysis of the regions showed the C 1s, Cl 2p and O 1s signals to be multi-component, presenting signals of the PVC, the plasticizer and the other additives. Binding energies remained constant irrespective of P-radiation dosage, but the amount of chlorine component at 198.4 +/- 0.1 eV (associated with modified PVC) decreased with sterilization dosage. Angle-resolved XPS revealed that this component is located at the outermost surface of the polymer. It can be hypothesized that the production processes themselves (extrusion and/or injection molded) already induce modifications of the polymer surface and also lead to surface segregation of the plasticizer. During the subsequent thermal sterilization of the polymer dehydrochlorination continues but, because of the very short time required by the beta-irradiation technology to sterilize devices, the atmospheric oxygen is unable to diffuse into the irradiated material, thus inhibiting further side-degradation of the materials, such as thermo-oxidative degradation. Copyright
2003
- Radiation-induced migration of additives in PVC-based biomedical disposable devices. Part 1. Surface morphology by AFM and SEM/XEDS
[Articolo su rivista]
M., Manfredini; D., Atzei; Marchetti, Andrea; B., Elsener; M., Malagoli; F., Galavotti; Rossi, Aldo
abstract
Two different types of plasticized poly(vinyl chloride) (PVC) used for biomedical disposable devices-extruded and injection moulded-were studied in the non-sterilized condition and after 25 and 50 kGy of beta irradiation. The polymer surfaces were analysed by scanning electron microscopy (SEM) equipped with an x-ray energy-dispersive spectroscopy (XEDS) and by atomic force microscopy (AFM). The inner surface of two parts of a venous line showed a different morphology according to their original formulation (for extrusion or injection moulding process) and reacted differently on sterilization with beta irradiation. Moulded parts were affected only slightly by the radiation step, whereas the variations were bigger for the extruded parts. In order to gain the best performances for the medical devices studied, the utmost care must be taken in the sterilization step, which should be optimized as well as the other steps of the manufacturing process. Copyright
2003
- Refractive properties of binary mixtures containing 1,2-dichloroethane + 2-methoxyethanol or 1,2-dimethoxyethane
[Articolo su rivista]
M., Manfredini; Marchetti, Andrea; S., Sighinolfi; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Refractive index (n) and related properties such as molar refraction (R) have been investigated for DCE + ME and DCE + DME binary mixtures over the entire composition range, at different temperatures in the interval 0 less than or equal to t / degreesC less than or equal to 70. Some empirical and theoretical relationships have been applied to study the dependence of the measured and derived quantities on temperature and on binary composition. Furthermore, the excess functions n(E), R-E and the excess Kirkwood correlation parameters Deltag have been examined, in order to identify the presence of solvent-cosolvent adducts in these binary solvent systems. The results obtained have been interpreted on the basis of specific intermolecular interactions between different species. (C) 2003 Elsevier Science B.V. All rights reserved.
2003
- Selective solvation of chiral compounds in binary mixtures of 2-butanone + 2-butanol
[Relazione in Atti di Convegno]
Faranda, S; Foca, Giorgia; Manfredini, Matteo; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo
abstract
-
2003
- Solvatazione selettiva di biomolecole in miscele binarie 2-butanone + 2-butanolo
[Relazione in Atti di Convegno]
Foca, Giorgia; Manfredini, Matteo; Manzini, Daniela; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo; Zucchi, Claudia
abstract
-
2003
- Viscosimetric properties and internal structure of N,N-dimethylformamede+1,2-dimethoxyethane binary mixtures
[Articolo su rivista]
Cocchi, Marina; M., Manfredini; D., Manzini; Marchetti, Andrea; S., Sighinolfi; Tassi, Lorenzo; Ulrici, Alessandro; M., Vignali; Zannini, Paolo
abstract
The kinematic viscosities (v) of liquid binary mixtures of N,N-dimethylformamide and 1,2-dimethoxyethane were measured at 19 temperatures in the range -10 less than or equal to t / degreesC less than or equal to 80, employing the pure species and 9 their solutions covering the whole miscibility range expressed by the condition 0 less than or equal to x(i) less than or equal to 1. The measured values have been used to test some empirical equations of the type v=v(T), v=v(x(i)), and v=v(T,x(i)), in order to obtain useful correlation models with predictive ability in correspondence of the experimental data gaps. Starting from the experimental data, the excess kinematic viscosities (v(E)) have been calculated. Sign and magnitude of these quantities have been discussed in terms of type and nature of specific intermolecular interactions. Some derived quantities such as thermodynamic parameters of the viscous flow (DeltaG*, DeltaH* and DeltaS*), have been calculated on the basis of Eyring's model. Furthermore, the fluidity of this binary solvent system was analysed and interpreted following Hildebrand and modified-Hildebrand correlation models. (C) 2003 Elsevier Science B.V. All rights reserved.
2002
- Beta-functionalised polythiophenes as microelectrode modifiers in low conductive media
[Articolo su rivista]
Cocchi, Marina; Franchini, Giancarlo; M., Manfredini; Marchetti, Andrea; Pigani, Laura; Seeber, Renato; Tassi, Lorenzo; Ulrici, Alessandro; M., Vignali; Zanardi, Chiara; Zannini, Paolo
abstract
A study on polythiophene coated microelectrodes is reported, the goal being that of checking the capability of these electrochemical systems to work in low conductive media. The possibility of electrochemically p-doping the polymer in the presence of very low concentrations or even in the absence of supporting electrolyte in the solution is ascertained, opening the way to the use of similar systems in pure solvent media. This result is obtained in such conditions that the presence of residual charges - and corresponding counterions - trapped inside the film coating can be reasonably hypothesised.
2002
- Caratterizzazione di farine di frumento mediante analisi PCA di spettri infrarossi
[Articolo su rivista]
Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
La qualità risulta essere un criterio fondamentale per la scelta dei prodotti alimentari da parte dei consumatori, pertanto le tecniche anaitiche che si occupano del controllo della composizione chimica degli alimenti e dell'individuazione di eventuali adulterazioni sono in continuo aumento.
2002
- Classificazione di spettri MIR acquisiti su matrici di origine cerealicola mediante l’utilizzo dell’algoritmo WPTER
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
-
2002
- Densities and excess molar volumes of binary mixtures containing 1,2-dichloroethane + 2-methoxyethanol or 1,2-dimethoxyethane at different temperatures
[Articolo su rivista]
M., Manfredini; Marchetti, Andrea; S., Sighinolfi; Tassi, Lorenzo; Ulrici, Alessandro; M., Vignali
abstract
Density of the 1,2-dichloroethane + 2-methoxyethanol or 1,2-dimethoxyethane binary mixtures have been measured at different temperatures over the complete composition range. Several experimental measurements have been used to check the validity of the relationships accounting for the dependence of the density on temperature and composition, useful to obtain interpolated values in correspondence of the experimental data gaps. Starting from the primary data, some derived quantities, such as partial molar volumes, excess and partial excess molar volumes, have been obtained. In these mixtures, V-E is always positive for DCE + ME binaries, while an S-shaped dependence on composition at each temperature is obtained in DCE + DME system, showing positive values in the DCE rich-region and negative values at the opposite extreme. The results are compared and discussed to shed some light to the changes in molecular association and structural effects in these binary solvent systems.
2002
- Density, refractive index, and related properties for 2-butanone plus n-hexane binary mixtures at various temperatures
[Articolo su rivista]
Baraldi, Pietro; M. G., Giorgini; M., Manfredini; D., Manzini; Marchetti, Andrea; Tassi, Lorenzo
abstract
Density refractive index n and the related properties molar volume V and molar refraction R have been investigated for 2-butanone + n-hexane liquid binary mixtures over the entire composition range and a wide range of temperatures. Some well-known relationships have been applied to study the temperature and composition dependence of the measured and derived quantities. Furthermore, the deviations of the respective excess properties V-E, n(E), and R-E have been examined, with the aim of identifying particular intermolecular interaction patterns responsible for the macroscopic behavior of these binary mixtures. The results have been interpreted on the basis of structural and geometric effects between the components.
2002
- Determination of carboxylic acids in vinegars and in aceto balsamico tradizionale di modena by HPLC and GC methods
[Articolo su rivista]
Cocchi, Marina; P., Lambertini; Manzini, Daniela; Marchetti, Andrea; Ulrici, Alessandro
abstract
The presence of carboxylic acids in grape products has been investigated for a long time by researchers, from both the qualitative and quantitative points of view. Evaluation of carboxylic acids requires the study and optimization of some operative variables which are strictly related to the matrix. In particular, the determination of organic acids in real matrixes such as Aceto Balsamico Tradizionale of Modena (ABTM; a traditional balsamic vinegar made from cooked grape must) is often difficult because of the presence of numerous interferences that need to be removed by separation techniques. To this aim, in the present work a solid-phase extraction (SPE) method with C18 and NH2 exchangers was used to clean the ABTM samples prior to analysis or further treatments. Both HPLC and GC techniques were used to determine organic acids. The efficiency of these two different analytical techniques in the study of ABTM acidic composition has been evaluated. Both methods separately were not able to supply all the data related to carboxylic acids. In particular, HPLC allows acetic and lactic acids quantification, but gluconic and succinic acids are better determined by GC. As far as tartaric, citric, and malic acids are concerned, both HPLC and GC methods give statistically equivalent results. The variation of the single acidic species composition along a series of casks furnished interesting information regarding the chemical transformations taking place during the aging process of this product.
2002
- Effetti della Sterilizzazione per Irraggiamento sulle Superfici di Materiali Plastici per Uso Bio Medicale
[Relazione in Atti di Convegno]
Cocchi, Marina; Manfredini, Matteo; Marchetti, Andrea
abstract
Comunicazione orale
2002
- Il sistema ternario metanolo + etanolo + 1-propanolo: proprietà volumiche e disegno sperimentale di miscele solventi
[Relazione in Atti di Convegno]
Cocchi, Marina; Foca, Giorgia; Franchini, Giancarlo; Manfredini, Matteo; Manzini, Daniela; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro; Vignali, M.
abstract
-
2002
- Kinematic viscosities of binary liquid mixtures of 2-butanone with 1,2-propanediol
[Articolo su rivista]
M., Manfredini; Marchetti, Andrea; S., Sighinolfi; Tassi, Lorenzo; Ulrici, Alessandro; M., Vignali; C., Zucchi
abstract
Kinematic viscosities of the binary 2-butanone (1) + 1,2-propanediol (2) solvent system have been measured for mixtures covering the whole miscibility range expressed by 0 less than or equal to x(i) less than or equal to 1, at 19 temperatures in the range -10 less than or equal to t/degreesC less than or equal to 80. The measured values have been used to test empirical equations that express the kinematic viscosities as functions of the composition and temperature. Excess kinematic viscosities (nu(E)) have also been calculated. Sign and magnitude of these quantities are discussed in terms of type and nature of specific intermolecular interactions. Furthermore, derived quantities such as thermodynamic parameters of viscous flow (DeltaGdouble dagger, DeltaHdouble dagger and DeltaSdouble dagger), are analyzed on the basis of Eyring's model. All the investigated excess mixing properties indicate the probable existence of stable two-component adducts in this binary solvent system.
2002
- Temperature and composition dependence of the refractive indices of the 2-chloroethanol + 2-methoxyethanol binary mixtures
[Articolo su rivista]
Cocchi, Marina; M., Manfredini; Marchetti, Andrea; Pigani, Laura; Seeber, Renato; Tassi, Lorenzo; Ulrici, Alessandro; M., Vignali; Zanardi, Chiara; Zannini, Paolo
abstract
AbstractMeasurements of the refractive index n for the binary mixtures 2-chloroethanol + 2-methoxyethanol in the 0 ≤ T/°C ≤ 70 temperature range have been carried out with the purpose of checking the capability of empirical models to express physical quantity as a function of temperature and volume fraction, both separately and together, i.e., in a two independent variables expression. Furthermore, the experimental data have been used to calculate excess properties such as the excess refractive index, the excess molar refraction, and the excess Kirkwood parameter Ag over the whole composition range. The quantities obtained have been discussed and interpreted in terms of the type and nature of the specific intermolecular interactions between the components.
2002
- Viscosity of (ethane-1,2-diol+1,2-dimethoxyethane + water) at temperatures from 263.15 K to 353.15 K
[Articolo su rivista]
Cocchi, Marina; M., Manfredini; Marchetti, Andrea; Pigani, Laura; Seeber, Renato; Tassi, Lorenzo; Ulrici, Alessandro; Zanardi, Chiara
abstract
AbstractThe kinematic viscosity ν for (ethane-1,2-diol + 1,2-dimethoxyethane + water) was measured at 14 different ternary compositions covering the whole miscibility field, and at 19 temperatures in the range 263.15 T / K 353.15. The experimental values were fitted using empirical equations of the type ν = ν (T) and ν = ν (xi), respectively, in order to provide reliable models to account for the behaviour of the system. The excess kinematic viscosity νEhas been determined and interpreted in terms of the type and nature of the interactions among the components of the mixture. Using the experimental ν data, the thermodynamic properties ( ΔG * , ΔH * ,ΔS * ) of the viscous flow have been obtained from the Eyring’s approach and standard thermodynamic equations. Furthermore, excess mixing functions, such asΔG * E , have been determined, and found to evidence the existence of quite strong specific interactions among the components, probably due to the formation of hydrogen bonds and dipolar networks. However, all the calculated excess mixing properties suggest the absence of stable three-component adducts.
2001
- Density and volume properties of the 2-methoxyethanol+1,2-dimethoxyethane + water ternary solvent system at various temperatures
[Articolo su rivista]
Cocchi, Marina; Marchetti, Andrea; Pigani, Laura; Tassi, Lorenzo; Ulrici, Alessandro; G., Vaccari; Zanardi, Chiara
abstract
Densities (rho) of the ternary mixtures 2-methoxyethanol + 1,2-dimethoxyethane + water have been measured at 19 temperatures in the range -263.15 less than or equal toT/K less than or equal to 353.15. The experimental data were processed by empirical relations accounting for the dependence of rho on temperature and ternary composition expressed as mole fraction of the components (0 less than or equal to x(i) less than or equal to 1). All checked equations seem to be suitable for correlation purposes, in order to obtain interpolated values in correspondence to experimental data gaps. Furthermore, the excess molar volume (V-E) has been investigated to make evident the possibility of forming stable solvent-cosolvent adducts. The excess property has been interpreted on the basis of specific intermolecular interactions between the components.
2001
- Refractive properties of binary mixtures containing N,N-dimethylformamide+2-methoxyethanol or 1,2-dimethoxyethane
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; Seeber, Renato; Tassi, Lorenzo; Zannini, Paolo
abstract
Refractive index (n) and related properties such as molar refraction (R) have been investigated for DMF+ME and DMF+DME binary mixtures over the entire composition range, at 15 different temperatures in the range 0 less than or equal to t/degreesC less than or equal to 70. Some relationships have been applied to study the dependence of the measured and derived quantities by temperature and composition. Furthermore, the excess functions n(E), R-E and the excess Kirkwood correlation parameters Deltag have been examined, in order to identify the presence of solvent-cosolvent adducts in these binary mixtures. The results obtained have been interpreted on the basis of specific intermolecular interactions between different species.
2001
- The 2-Methoxyethanol + 1,2-Dimethoxyethane + Water Ternary System: Static Relative Permittivity from -10 to 80 °C
[Articolo su rivista]
Cocchi, Marina; DE BENEDETTI, Pier Giuseppe; Marchetti, Andrea; Menziani, Maria Cristina; Seeber, Renato; Tassi, Lorenzo; Ulrici, Alessandro
abstract
Static relative permittivities of the 2-methoxyethanol + 1,2-dimethoxyethane + water ternary solvent system were measured as a function of temperature (-10 less than or equal to t/degreesC less than or equal to 80) and of composition, over the whole molar fractions range 0 less than or equal to x(1), x(2), x(3) less than or equal to 1. The experimental values have been used to test some empirical relationships accounting for the dependence of epsilon on T. x(i), and on T, x(i) couples of values. A comparison between calculated and experimental data shows that these relationships can be profitably employed to predict E values in correspondence to experimental data gaps. The excess dielectric permittivity, epsilon (E), assumes, in the most cases, negative values for any compositions of the mixtures. while the values of the excess molar polarization, PE, are positive. The large values of the excess quantities are indicative of the strong specific interactions among similar, as well as different molecules in the mixtures. Discussion of the data in terms of Kirkwood correlation factor also gives information on the short-range intermolecular interactions among the components. suggesting the formation of two-components adducts rather than of than mure complex moieties involving all three molecular species.
2001
- The Ethane-1,2-diol + 2-Methoxyethanol + 1,2-Dimethoxyethane Ternary Solvent System: Density and Volume Proprties at Different Temperatures.
[Articolo su rivista]
Cocchi, Marina; M., Manfredini; Marchetti, Andrea; Sighinolfi, Simona; Tassi, Lorenzo; Ulrici, Alessandro; M., Vignali
abstract
The density of the ethane-1,2-diol+2-methoxyethanol + 1,2-dimethoxyethane ternary mixtures has been measured at different temperatures ranging from-10 to 80° C, and over the whole composition range. The experimental data have been used to check the validity of some relationships accounting for the dependence of the density on temperature and composition, useful to evaluate the behaviour of this property in the whole temperature and composition domains. Starting from the primary data, some derived quantities, such as excess molar volumes, partial molar volumes and partial excess molar volumes, have been obtained. In these mixtures VE is generally negative at all the experimental conditions, showing the greatest deviations along the binary axes corresponding to the binary subsystems. The results are compared and discussed to get light to the changes in molecular association and structural effects in this solvent system.
2001
- Valutazione di Modificazioni Superficiali Indotte dalla Sterilizzazione per Irraggiamento di Materiali Plastici per Uso Biomedicale
[Relazione in Atti di Convegno]
Manfredini, Matteo; Manzini, Daniela; Marchetti, Andrea; Atzei, D.; Rossi, A.
abstract
Comunicazione orale
2000
- Density and volume properties of ethane-1,2-diol + 1,2-dimethoxyethane + water ternary mixtures from -10° to 80°c
[Articolo su rivista]
Baraldi, Pietro; Franchini, Giancarlo; Marchetti, Andrea; G., Sanna; Tassi, Lorenzo; Ulrici, Alessandro; G., Vaccari
abstract
Thermodynamic interactions in the ethane-1,2-diol (1) + 1,2-dimethoxyethane (2) + water (3) ternary system have been investigated in terms of the excess molar volume, derived from density measurements at 19 different temperatures from -10 degrees to 80 degrees C. Fourteen three-component mixtures have been considered, covering the entire composition range. The excess molar volumes are discussed in terms of conformational changes induced in each component by the presence of another one. The results obtained support the hypothesis of the absence of any three-component complex adducts under all experimental conditions investigated.
2000
- Density and volumetric properties of ethane-1,2-diol plus di-ethylen-glycol mixtures at different temperatures
[Articolo su rivista]
Cocchi, Marina; Marchetti, Andrea; Pigani, Laura; G., Sanna; Tassi, Lorenzo; Ulrici, Alessandro; G., Vaccari; Zanardi, Chiara
abstract
The density of the ethane-1,2-diol (ED) + di-ethylen-glycol (DEG) binary mixtures has been measured at different temperatures over the complete composition range. The experimental measurements have been used to check the validity of relationships accounting for the dependence of the density on temperature and composition, useful to obtain interpolated values in the correspondence of the experimented data gaps. Starting from the primary data, some derived quantities, such as partial molar volumes, excess and partial excess molar volumes, have been obtained. In these mixtures, V-E presents an S-shaped dependence on composition at each temperature, showing negative values in the ED rich-region and positive values at the opposite extreme. The results are compared and discussed to get light to the: changes in molecular association and structural effects in this solvent system. (C) 2000 Elsevier Science B.V. All rights reserved.
2000
- Determinazione di Metalli in Sostanze di Abuso Mediante Spettrometria GFAAS con Campionamento Solido
[Relazione in Atti di Convegno]
Marchetti, Andrea; Franchini, Giancarlo; Zannini, Paolo; Fazio, F. De; Licata, Manuela
abstract
Comunicazione Orale
2000
- Variation of volumic properties with temperature and composition of 2-butanone+1,2 propanediol binary mixtures
[Articolo su rivista]
Marchetti, Andrea; Palyi, Gyula; Tassi, Lorenzo; Ulrici, Alessandro; Zucchi, Claudia
abstract
In this work we present experimental values of the density (rho), and some related quantities such as excess molar volumes (V-E), of the 2-butanone + 1,2-propanediol binary mixtures at various temperatures in the -10 less than or equal to t / degreesC less than or equal to 80 range and as a function of mole fraction. The experimental results have been fitted to some relationships of the type rho = rho (T), rho = rho (x(i)), and rho = rho (T,x(i)) to estimate the property in correspondence of the experimental data gaps. The observed behaviour has been interpreted on the basis of specific interactions and molecular features of the components. (C) 2000 Elsevier Science B.V. All rights reserved.
1999
- Density and excess molar volume values of binary mixtures of 2-chloroethanol + 1,2-ethanediol
[Articolo su rivista]
FRANCHINI G., C; Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro; Vaccari, G.
abstract
Density of the 2-chloroethanol (CE) + 1,2-ethanediol (ED) binary solvent system are presented at 19 temperatures in the -10 < t/°C < 80 range. The measured values have been used to test some empirical equations of the type ro=ro(t), ro=ro(Xi) and ro=ro(t,Xi), in order to provide useful interpolation procedures to obtain calculated values corresponding to the experimental data gaps. From the primary data, the excess molar volumes (V^E) have been calculated. The sign and magnitude of this quantity have been discussed in term of the type and nature of binary interactions. Furthermore, the derived quantities have fitted the Redlich-Kister equation with very good accuracy. some
1999
- Kinematic viscosities of ternary mixtures containing ethane-1,2-diol, 2-methoxyethanol and water from-10 degrees C to 80 degrees C
[Articolo su rivista]
Cocchi, Marina; Marchetti, Andrea; G., Sanna; Tassi, Lorenzo; Ulrici, Alessandro; G., Vaccari
abstract
Kinematic viscosities (v) of the ternary ethane-1,2-diol (1) + 2-methoxyethanol (2)+ water (3) solvent system have been measured for 36 ternary mixtures covering the whole miscibility range expressed by the condition 0 <X-1,X-2,X-3 < 1, at 19 temperatures in the range - 10 less than or equal to t (degrees C) less than or equal to 80. The measured values have been used to test some empirical equations of the type v = v(t) and v = v(X-i), in order to provide for useful interpolation procedures to obtain calculated values in correspondence to the experimental data gaps. From the experimental data, the excess kinematic viscosities (v(E)) have been calculated. Sign and magnitude of these quantities have been discussed in terms of type and nature of specific intermolecular interactions. Furthermore, derived quantities such as thermodynamic parameters of the viscous flow (Delta G*, Delta H* and Delta S*), have been analysed on the basis of the Eyring's model. All the investigated excess mixing properties indicate the probable absence of stable three-component adducts in this ternary solvent system. (C) 1999 Elsevier Science B.V. All rights reserved.
1999
- Refractive indices of binary mixtures of (1,2-dichloroethane + 2-chloroethanol) at various temperatures
[Articolo su rivista]
Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro; Vaccari, Giulia; G., Sanna
abstract
Measurements of the refractive index n(D) of(1,2-dichloroethane + 2-chloroethanol) in the temperature range 273.15 K less than or equal to T less than or equal to 343.15 K have been carried out for the purpose of checking the suitability of some empirical models of the type n(D) = n(T), n = n(x(i)), and n = n(T, x(i)) for the correlation and interpolation of experimental data to cover existing gaps. Furthermore, the experimental data have been used to calculate excess properties such as Delta n(D), R-E, and the excess Kirkwood parameter ag over the entire composition range. The results obtained have been discussed and interpreted in terms of the type and nature of the specific intermolecular interactions between the components.
1998
- Densities and excess molar volumes of the solvent (ethane-1,2-diol + 2-methoxyethanol + water) from T = 263.15 K to T = 353.15 K
[Articolo su rivista]
Marchetti, Andrea; Martignani, Alberto; Tassi, Lorenzo
abstract
Densities rho are reported for {ethane-1,2-diol (1) + 2-methoxyethanol (2) + water (3)} at 19 temperatures ranging from T = (263.15 to 353.15)K on 36 ternaries of different mole fractions covering the whole miscibility field 0 < x(1)/x(2)/x(3) < 1. The experimental data have been used to test some empirical equations expressing the functions rho = rho(T) and rho = rho(x(1), x(2), x(3)), and the excess molar volumes V-E have been derived and used to investigate the presence of three component stable adducts in these mixtures.
1998
- Density and excess molar volumes of binary mixtures of 1,2-dichloroethane plus 2-chloroethanol from -10 to 80 degrees C
[Articolo su rivista]
Marchetti, Andrea; A., Martignani; Tassi, Lorenzo
abstract
Densities (rho) were measured for the 1,2-dichloroethane (DCE) + 2-chloroethanol (CE) at 19 temperatures in the range -10 less than or equal to t/C-0 less than or equal to 80. The experimental data were used to test some empirical relations giving the dependence of the density on the temperature and binary composition: rho = rho(t), rho = rho(X-1) and rho = rho(t, X-1). From the experimental data, the excess molar volumes (V-E) were calculated. The VE values are always positive. This quantity has been interpreted in terms of geometric effects (interstitial accomodation) and possible specific interactions (hydrogen bonding and dipolar interactions) which occur between components.
1998
- L`Aceto Balsamico e la Tradizione Scientifica
[Altro]
Franchini, Giancarlo; Marchetti, Andrea; Tassi, Lorenzo
abstract
L'Aceto Balsamico Tradizionale di Modena si presenta come un liquido sciropposo, denso, acetoso, di colore scuro, acido e dolce allo stesso tempo, dotato di un aroma fragrante e tipico. La particolare tecnica produttiva prevede: i) la cottura del succo d’uva, ottenuto da uve tipiche selezionate, per la preparazione del mosto cotto, ii) un processo di acetificazione a partire dal mosto cotto, iii) una fase di invecchiamento entro vaselli, botticelle di legni pregiati, effettuando rincalzi annuali sino al completamento della maturazione1, con conseguente affinamento delle caratteristiche organolettiche tipiche del prodotto.
1998
- The 2-methoxyethanol+1,2-dimethoxyethane binary solvent system. Refractive index and related properties from 0 to 70°C
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; Tassi, Lorenzo; G., Vaccari
abstract
The refractive properties of binary system containing 2-methoxyethanol (ME) and 1,2-dimethoxyethane (DME) have been measured at 15 temperatures in the range, working with the two pure species and 9 mixtures of them, covering the whole miscibility field ( ). Many equations have been checked in order to establish the best relationships stating the dependence of n on temperature and binary composition, by taking into account both the mole fraction (rational) scale and the volume fraction scale. Furthermore, the excess functions nE and RE (excess molar refraction) have been evaluated in order to investigated the existence of solvent-cosolvent complex adducts. As an evidence, we can suggest the presence of two complex moieties, namely 1ME 1DME and 2ME 1DME, which seem to be both thermostable at all investigated temperatures.
1997
- Density and volumetric behavior of 1,2-dimethoxyethane plus water binary mixtures from -10 to 80 degrees C
[Articolo su rivista]
Marchetti, Andrea; Tassi, Lorenzo; Ulrici, Alessandro
abstract
The densities (rho) and excess molar volumes (V-E) for 1,2-dimethoxyethane + water binary mixtures were determined, when possible, at 19 different temperatures ranging from -10 up to +80 degrees C. The experimental measurements were used to test some empirical relations giving the dependence of the density on the temperature and binary composition: rho = rho(t), rho = rho(X-1), and rho = rho(t,X-1). Furthermore, the results of V-E calculations are discussed in terms of the influence of interactions between the components, of the order and degree of packing in the mixtures, and of the free-volume differences.
1997
- Viscosimetric studies on 2-methoxyethanol plus 1,2-dimethoxyethane binary mixtures from -10 to 80 degrees C
[Articolo su rivista]
F., Corradini; Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo
abstract
The kinematic viscosities (v) were measured for nine binary solvent mixtures of 2-methoxyethanol (ME) + 1,2-dimethoxyethane (DME) at nineteen temperatures ranging from -10 to + 80 degrees C. The experimental data have been used to test some empirical equations of the type v = v(T), v = v(X-1) and v = v(T, X-1). The viscosities of all the mixtures increase from the values of pure DME to that of ME as the mole fraction of ME increases, and always yield a negative excess property (v(E)) all the investigated temperatures. Furthermore, thermodynamic parameters of viscous flow have been evaluated on the basis of the Eyring theory. The excess flee energy of activation of viscous flow (Delta G(*E)) vs X-2 plot suggests the presence of a stable hetero-adduct, having ME : DME = 1 : 1 stoichiometric ratio.
1996
- Determination of Alkali and Alkaline Earth Metals in Aceto Balsamico Tradizionale di Modena by Flame Atomic Absorption Spectroscopy.
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; G. C., Franchini; C., Preti
abstract
An atomic absorption spectroscopic method is proposed for determination of alkali and alkaline earth metals in Aceto Balsamico Tradizionale di Modena, ABTM.
1996
- Static dielectric constants of 1,2-dichloroethane + 2-methoxyethanol + 1,2-dimethoxyethane ternary liquid mixtures from -10 to 80 °C
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo
abstract
Static dielectric constants (epsilon) were measured for mixtures of 12-dichloroethane (DCE, 1) + 2-methoxyethanol (ME, 2) + 1,2-dimethoxyethane (DME, 3) at 19 temperatures in the range -10 less than or equal to t/degrees C less than or equal to 80, employing 12 ternaries covering the whole composition range expressed by the mole fractions 0 < X(1), X(2), X(3) < 1. Empirical fitting equations of the type epsilon = epsilon(T), epsilon = epsilon(X(i)) and epsilon = epsilon(T,X(i)), which might be useful for correlation and interpolation procedures, were used to represent the experimental data. The excess mixing property epsilon(E) has been evaluated to investigate the presence of solvent-cosolvent adducts at each temperature. The quantity epsilon(E) has been found to be partly positive and partly negative in the ternary domain {X(1), X(2), X(3)}. As a consequence, it is possible to observe an isoline at epsilon(E) = 0 at each temperature. Such a line represents a large set of ternary mixtures having a pseudo-ideal dielectric behavior, even being formed by interacting components.
1996
- Volumetric behaviour of the ethane-1,2-diol+1,2-dimethoxyethane binary solvent system
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; C., Preti; Tassi, Lorenzo
abstract
Densities have been measured for 11 binary mixtures of ethane-1,2-diol (ED, component 1) + 1,2-dimethoxyethane (DME, component 2), whose composition covers the whole miscibility field (0 less than or equal to X(1) less than or equal to 1), at 19 temperatures in the range -10 less than or equal to t/degrees C less than or equal to +80. The experimental data were used to test some empirical relationships of the general form rho = rho(t), rho = rho(X(1)) e rho = rho(t,X(1)). Furthermore, the experimental densities have been converted into the corresponding excess molar volumes (V-E), which have been discussed and interpreted in terms of the specific intermolecular interactions. The V-E against X(2) plots suggest the presence at each temperature of a more stable heteroaggregated complex species, at a stoichiometric ratio ED:DME = 2:1.
1995
- ASSOCIATING BEHAVIOR OF MIXED LIQUIDS - DIELECTRIC-PROPERTIES OF THE ETHANE-1,2-DIOL+1,4-DIOXAN SOLVENT SYSTEM FROM -10-DEGREES-C TO +80-DEGREES-C
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; G., Tosi
abstract
The associating behaviour of ethane-1,2-diol (component 1)+1,4-dioxan (component 2) in their binary mixtures has been investigated through their dielectric properties. The experimental measurements of the relative permittivity (epsilon) in the temperature range -10 less than or equal to t/degrees C less than or equal to 80 for nine binary mixtures covering the whole miscibility field 0 less than or equal to X(1) less than or equal to 1 have been utilized to test empirical equations representing the functions epsilon = epsilon(T), epsilon = epsilon(X(1)) and epsilon = epsilon(T, X(1)) Furthermore, the excess mixing function, epsilon(E), has been evaluated to obtain qualitative and quantitative information about the possibility of 'solvent-cosolvent' complex formation.
1995
- Block "f" metal complexes with Benzodiazepines. Cytostatic and antiviral biological studies
[Articolo su rivista]
G. C., Franchini; Marchetti, Andrea; C., Preti; Tassi, Lorenzo; G., Tosi; Zannini, Paolo
abstract
n.d.
1995
- Density and volumic properties of N,N-dimethylformamide +2-methoxyethanol+1,2-dimethoxyethane liquid ternary mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo
abstract
Densities (rho) at various temperatures ranging from -10 up to +80 degrees C have been measured for N,N-dimethylformamide+2-methoxyethanol+1,2-dimethoxyethane ternary solvent system, employing 66 mixtures covering the whole miscibility field. Polynomial equations describing the dependence on temperature, rho=rho(t/degrees C), and molar composition, rho=rho(X(1),X(2)), have been checked. Furthermore, the excess molar volumes (V-E), derived from rho values, can provide useful suggestions about the formation of solvent-cosolvent complexes. Excess molar volumes have been interpreted on the basis of specific interactions between unlike molecules, taking into account geometric effects and steric hindrances. The V-E quantities have been isothermally fitted by an empirical relation of the type V-E=V-E(X(1),X(2),X(3)) formally derived from the well known Redlich-Kister equation. As a rule, for all the here tested relationships, the calculated values agree very well with the experimental ones, indicating that all the equations can be safely employed fdr predictive calculations in correspondence of the experimental data gaps.
1995
- Dielectric characterization of binary solvents containing 1,2-dichloroethane and 2-chloroethanol
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; A., Varini
abstract
Static dielectric constants (epsilon) were determined for the 1,2-dichloroethane (DCE, 1)/2-chloroethanol (CE, 2) binary solvent system at 19 temperatures ranging from -10 to +80 degrees C and in the whole composition range expressed by the mole fraction 0 less than or equal to X(1) less than or equal to 1. The experimental values have been fitted to some equations that could be usefully employed for predictive epsilon calculations. Furthermore, the excess mixing properties (epsilon(E)) have been evaluated in order to point out the presence of solvent-cosolvent adducts in the binary mixtures mentioned above. The values of epsilon(E) have been generally found to be negative and only slightly positive under a few experimental conditions in the CE rich-region, thus giving evidence of a close interaction network probably via hydrogen bonding as well as other interactions of every kind in this solvent system.
1995
- Dielectric properties of binary mixtures of 1,2-dichloroethane plus ethane-1,2-diol and 1,2-dichloroethane plus 2-methoxyethanol
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; C., Preti; M., Tagliazucchi; Tassi, Lorenzo
abstract
The dielectric behaviour of binary mixtures of 1,2-dichloroethane (DCE)/ethane-1,2-diol (ED) and DCE/2-methoxyethanol (ME) has been studied at 19 temperatures in the range from -10 to +80 degrees C. The DCE/ED system is immiscible, except in a narrow range near the ED-rich region. The DCE/ME system, which is completely miscible, has been investigated over the whole composition range. Fitting procedures have been applied in order to check the suitability of empirical or semiempirical functions of the type epsilon(T), epsilon(X(i)) and epsilon(T,X(i)). Furthermore, the excess static dielectric constant, epsilon(E), has been evaluated in order to investigate the possibility of the existence of complex entities. A DCE.2ME species appears to be the only stable adduct.
1995
- Investigation on the viscosi metric properties of 1,2-ethanediol+1,2-dimethoxyethane binary mixtures
[Articolo su rivista]
Corradini, Fulvio; Marchetti, Andrea; Tagliazucchi, Mara; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The kinematic viscosity of pure ethane 1,2-diol, 1,2-methoxyetane and nine binary mixture at 19 temperatures ranging from -10 to 80 C has been measured.
1995
- Static dielectric constants of 1,2-dichloroethane + 1,2-dimethoxyethane binary mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo
abstract
Static dielectric constants (epsilon) have been measured for pure 1,2-dichloroethane, 1,2-dimethoxyethane, and for 9 of theirs binary mixtures over the entire composition range and at 19 temperatures ranging from -10 up to +80 degrees C. The experimental data have been fitted by some empirical or quasi-theoretical equations of the type epsilon=epsilon(T), epsilon=epsilon(X(1)), and epsilon=epsilon(T,X(1)). Furthermore, the shift from ideality has been taken into account and evaluated on the basis of excess function epsilon(E) Positive deviations are detected at all experimental conditions, and a maximum occurs in the excess quantity, showing the existence of a stable solvent-cosolvent complex adduct at the stoichiometric ratio DCE : DME = 1 : 1, which may be interpreted in terms of moderately weaker interactions such as dipolarity and polarizability between dissimilar molecules.
1995
- The 1,2-dimethoxyethane - water solvent system. Viscokinetic and thermodynamic properties of viscous flow from -10 to 80 °C
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; A., Varini
abstract
Kinematic viscosity (v) has been measured for pure 1,2-dimethoxyethane, and for nine of its binary mixtures with water, covering the whole miscibility field, and working at 19 temperatures in the -10 less than or equal to t/degrees C less than or equal to 80 range. The properties investigated have been fitted by some empirical equations of the type v=v(T) and v=v(X(1)). Starting from the experimental viscosities, the thermodynamic parameters (Delta G*, Delta H*, Delta S*) of the viscous flow in these binaries have been obtained by applying the Eyring approach and the standard thermodynamic equations. Furthermore, the excess functions, such as v(E) and Delta G(*E) have been evaluated, showing the existence of quite strong specific interactions between the components, probably via hydrogen bonding and a dipolar network. Experimental variations in the Delta G(*E) quantity with temperature were very useful in order to depict and differentiate the trend in three well defined composition regions, namely M(I), M(II), and M(III), which are probably characterized by different patterns in molecular aggregation between similar and/or non similar species.
1995
- The N,N-dimethylformamide + 2-methoxyethanol binary mixtures. Viscosity and activation energy of viscous flow at various temperatures
[Articolo su rivista]
F., Corradini; Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo
abstract
Dynamic viscosity (eta) of binary solvent mixtures of N,N-dimethylformamide (DMF, component 1)+ 2-methoxyethanol (ME, component 2) has been investigated at 19 temperatures ranging from -10 to +80 degrees C. Some empirical equations have been applied in order to establish the best regression fitting procedures eta=eta(T), eta=eta(X(1)) and eta=eta(T,X(1)). For this binary solvent system, the viscometric properties are continuous but not linear functions of the mixture composition. Therefore, experimental eta values were used to calculate the excess viscosities (eta(E)) and excess Gibbs activation energies (Delta G*(E)) of viscous flow. Both these quantities strongly deviate from ideality over the whole composition range of the investigated mixtures. Furthermore, deviations from the ideal behaviour could be very useful in order to evidentiate the formation of solvent-cosolvent complex species and to evaluate their stoichiometrical composition.
1995
- Thermodynamics of viscous flow in ethane-1,2-diol + water binary mixtures.
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Kinematic Viscosities (nu) of pure ethane-1,2-diol (component 1) and of nine mixtures with water (component 2) were measured at 19 temperatures ranging from -10 to +80 degrees C, and for binary compositions covering the whole miscibility field expressed by the relation 0 less than or equal to X(1) less than or equal to 1. The property fitted some empirical equations in terms of the dependences nu = nu(T) and nu(X(1)), where T is the thermodynamic temperature and X(1) is the mole fraction of ethane-1,2-diol. Furthermore, the excess function (nu(E)) and the excess Gibbs energy of activation of viscous flow (Delta G*(E)) have been investigated. The trend of nu(E) against binary composition of the mixtures shows negative deviations from ideal behaviour, while the contrary is true for Delta G*(E) The results indicate specific molecular interactions between the components, and an overview is given on the basis of the molecular dynamics of the pure species.
1994
- 2-methoxyethanol - water solvent system : static relative permittivity from -10 to 80°C
[Articolo su rivista]
F., Corradini; Marcheselli, Luigi; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
A detailed dielectric study of 2-methoxyethanol (ME)-water (W) mixtures has been carried out as a function of temperature in the range - 10 to + 80-degrees-C and over the entire binary composition range (0 less-than-or-equal-to x less-than-or-equal-to 1). The experimental data, obtained by the heterodyne beat method at 2 MHz, were used to test some empirical relations of the type epsilon = epsilon(T), epsilon = epsilon(x) and epsilon = epsilon(T, x), in order to assess the empirical performances in dielectric behaviour of these mixtures, including the experimental conditions which are able to modify such patterns. The data reported here for ME-W binary mixtures were useful trying to understand the relative discriminating ability of both components towards cooperative intermolecular interactions in the liquid state, the quantitative similarities and differences between the chosen pure species, the intermolecular phenomena and interactions influencing the dielectric properties of the mixtures and the usefulness of a qualitative description of the possible formation of solvent-cosolvent complex species involving hydrogen-bonding, dipole-dipole and other interactions.
1994
- ANALYSIS OF HEAVY-METALS IN ACETO-BALSAMICO-TRADIZIONALE-DI-MODENA BY FLAME ATOMIC-ABSORPTION SPECTROSCOPY
[Articolo su rivista]
Corradini, F; Marcheselli, Luigi; Marchetti, Andrea; Preti, Carlo; Biancardi, C.
abstract
A detailed investigation of Aceto Balsamico Tradizionale di Modena (ABTM) was carried out. The necessity of knowing the metal content of this original and widely used product is of great importance. Measurements were carried out on a large number of samples of different ages to check the dependence of metal content on product aging.
1994
- DENSITIES AND EXCESS MOLAR VOLUMES FOR BINARY-MIXTURES OF N,N-DIMETHYLFORMAMIDE PLUS 1,2-DIMETHOXYETHANE
[Articolo su rivista]
F., Corradini; Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Densities p are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from -10 to 80-degrees-C. The experimental density data have been filled by empirical relations and the excess volumes by a Redlich-Kister equation. The 1:1 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.
1994
- Dielectric behaviour of the N,N-dimethylformamide + 2-methoxyethanol + 1,2-dimethoxyethane ternary solvent system from -10° to + 20°C
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The static relative permittivities, epsilon, and excess properties, epsilon(E), of the ternary mixtures N,N-dimethylformamide (DMF)-2-methoxyethanol (ME)-1,2-dimethoxyethane (DME) have been measured at several temperatures in the range -10 to +20-degrees-C. This ternary system shows interesting properties for use as a mixed solvent and for electroanalytical applications. The study of these mixtures should help to increase our understanding of the co-solvation of ionizable and inert solutes. The behaviour of epsilon(E) is quite interesting because this quantity assumes partly positive and partly negative values in the composition domain. As a consequence, there are mixtures which have epsilon(E) = 0, indicating ideal dielectric mixing behaviour. The excess property is discussed in terms of the influence of specific interactions between components, the order and degree of packing in the mixtures and any other effects which produce long-range structure in these mixed liquids.
1994
- Electrolytic dissociation of sodium tetraphenylborate in 2-methoxyethanol / water binary solvent mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Thermodynamic properties from conductance data are reported for the NaBPh4 electrolytic solutions in 2-methoxyethanol (component 1)/water (component 2) binary solvent mixtures, working at 19 temperatures ranging from -10 to +80-degrees-C and for 6 mixtures covering the 0.1865 less-than-or-equal-to x1 less-than-or-equal-to 1 composition range. Experimental conductivity data were analysed using the Fuoss-Hsia equation, and the chosen salt was found to associate to a certain extent in these solvent mixtures. The resulting dissociation constants (K) of the ion-pair have been used to test some empirical equations K = K(T), K= K(x1), and K = K(T, x1). Furthermore, the present findings have been compared with our previously reported results from working with picric acid in the same mixtures and experimental conditions.
1994
- INVESTIGATIONS ON THE VISCOMETRIC PROPERTIES OF ETHANE-1,2-DIOL+1,2-DIMETHOXYETHANE BINARY-MIXTURES
[Articolo su rivista]
Corradini, F; Marchetti, Andrea; Tagliazucchi, M; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The kinematic viscosity (nu) of pure ethane-1,2-diol (ED), 1,2-dimethoxyethane (DME) and nine binary mixtures at nineteen temperatures ranging from -10 to +80-degrees-C has been measured. The experimental values have been used to test some empirical equations of the type nu = nu(T) and nu = nu(x1), which are also suitable for data fits in the case of strongly associated dipolar components in the mixtures. The chainlike self-association of ED is widely reflected in its viscosity, which is considerably greater than that of DME. The viscosities of all the mixtures increase on passing from the values of pure DME to pure ED as the mole fraction of ED increases, and the mixing process always gives rise to negative excess properties (nu(E)) at all the temperatures investigated. Furthermore, thermodynamic parameters of viscous flow have been evaluated on the basis of Eyring's theory.
1994
- Investigations of viscometric properties of 1,2-ethanediol + 1,2-dimethoxyethane binary mixtures
[Articolo su rivista]
Corradini, F.; Marchetti, Andrea; Tagliazucchi, M.; Tassi, Lorenzo; Tosi, G.
abstract
Kinematic Viscosities of pure ethane-1,2-diol (ED,1) and of nine mixtures with 1,2-dimethoxyethane (DME, 2) were measured at 19 temperatures ranging from -10 to +80 °C, and for binary compositions covering the whole miscibility field expressed by the relation 0 less than or equal to X(1) less than or equal to 1. The property fitted some empirical equations in terms of the dependences nu = nu(T) and nu(X(1)). Furthermore, the excess function (nu(E)) and the excess Gibbs energy of activation of viscous flow (Delta G*(E)) have been investigated. The trend of nu(E) against binary composition of the mixtures shows negative deviations from ideal behaviour. The results indicate specific molecular interactions between the components, and an overview is given on the basis of the molecular dynamics of the pure species.
1994
- The relative permittivity of the ternary 1,2-ethanediol + 2-methoxyethanol + water solvent system
[Articolo su rivista]
F., Corradini; Marcheselli, Luigi; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
For many multicomponent cosolvent systems which can be important in electrochemical studies as far as in practical applications, the relative permittivity (epsilon) is a continuous but nonlinear function of the solvent composition. Rational functions were applied to the 1,2-ethanediol (1)+2-methoxyethanol (2)+water (3) ternary mixtures data at various temperatures (50 less-than-or-equal-to t/degrees-C less-than-or-equal-to 80) instead of the more conventional polynomial regressions for epsilon=epsilon(X(i)). These rational functions seem to be more adequate than the other polynomials, being reduced the number of required adjustable coefficients; in fact only a first power dependence on mole fraction (X(i)) is necessary, and a computational simplicity in reproducing reliable epsilon values over the total mole fraction 0 less-than-or-equal-to X1/X2/X3 less-than-or-equal-to 1 range is achieved. Furthermore, the calculated excess function (epsilon(E))is always negative, confirming the existence of rather strong interaction between components, probably via hydrogen bonding networks. Changes with temperature in epsilon(E) for these ternary mixtures seem to be very useful in order to depict and differentiate the experimental trend in three well distincted regions (namely M(I),M(II),M(III)) which are likely characterized by different specific interactions between like and/or unlike species. Nevertheless, no evidence for a three component adduct was obtained.
1994
- Thermodynamic analysis of viscosity data of ethane-1,2-diol + 1,4-dioxan binary mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Kinematic viscosities (nu) have been measured for pure ethane-1,2-diol, 1,4-dioxan and for nine of their mixtures covering the entire composition range and, where possible, at 19 temperatures from -10 to +80-degrees-C. The experimental values were converted into dynamic viscosities (eta) and were correlated with temperature and binary composition by some empirical equations. Furthermore, the excess function eta(E) and the excess Gibbs energy of activation of viscous flow DELTAG*E have been evaluated. Negative deviations from ideality are always observed for this binary system, this fact indicating strong specific interactions between unlike entities in solution to form stable solvent-cosolvent adducts. Activation enthalpies and entropies for viscous flow have been derived, and their dependence on binary composition is also discussed.
1994
- Transport and structural properties of alkali-metal bromides in 2-methoxyethanol solutions
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Limiting molar conductivity data for alkali-metal bromides MBr (M=Li, Na, K, Rb, Cs) in 2-methoxyethanol solutions at 19 different temperatures in the -10 less-than-or-equal-to t/degrees-C less-than-or-equal-to 80 range have been used to test some correlation functions. The LAMBDA0 values have been apportioned into individual ionic contributions (lambda0,i) using the tetraphenylphosphonium tetraphenylborate reference electrolyte method, and the temperature dependence of these quantities follows the equation of Speedy and Angell, lambda0,i = A0(T/T(S) - 1)gamma. The activation energies for ionic mobilities have been evaluated from the Arrhenius equation, providing evidence that in these solutions the ionic migration at 25-degrees-C of cations and anions follows the sequences Na+ < PPh4+ < Li+ congruent-to K+ < Rb+ < Cs+ and BPh4- < Br- respectively. Other quantities such as ionic radii in solution and solvation numbers have been derived by applying literature approaches.
1994
- Volumetric behaviour of 2-methoxyethanol + 1,2-dimethoxyethane binary mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Thermodynamic interactions in 2-methoxyethanol (component 1)+1,2-dimethoxyethane (component 2) binary mixtures have been studied in terms of the excess molar volume from the densities, measured at 19 temperatures between -10 and 80-degrees-C, for nine binary mixtures covering the whole miscibility field expressed by the mole fraction 0 less-than-or-equal-to X1 less-than-or-equal-to 1. Excess molar volumes are discussed in terms of induced conformational changes in each component in the presence of the other. The present findings support a hypothesis about the formation of a solvent-cosolvent complex species which has a well defined 1:1 stoichiometric composition and is thermostable under the experimental conditions.
1993
- A NON-LINEAR CORRELATION MODEL FOR THE RELATIVE PERMITTIVITY OF TERNARY AMPHIPROTIC (SOLVENT) MIXTURES
[Articolo su rivista]
F., Corradini; Marcheselli, Luigi; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Relative permittivities (epsilon) were determined for ternary ethane-1,2-diol (component 1)/2-methoxyethanol (component 2)/water (component 3) mixtures at five temperatures ranging from 5 to 25-degrees-C and over the mole fraction composition range 0 less-than-or-equal-to X(i) less-than-or-equal-to 1. The data have been fitted to a model equation that could be useful for predictive epsilon calculations. From the measured epsilon values, the excess relative permittivity epsilon(E) has been evaluated in order to test for three-component adducts. The values of epsilon(E) have been found to be negative for all the ternary mixtures under all the experimental conditions, which suggests a strong interaction network through hydrogen bonding, although evidence for a discrete three-component adduct was not forthcoming.
1993
- Conductances of sodium tetraphenylborate in 2-methoxyethanol - water binary solvent mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Conductance measurements have been carried out on the mixed 2-methoxyethanol (component 1)-water (component 2) solvent system for NaBPh4 solutions at 19 temperatures ranging from - 10 to + 80-degrees-C, and for six binary solvent mixtures covering the 0.1865 less-than-or-equal-to x1 less-than-or-equal-to 1 mole fraction range. The experimental data were processed by the more general Fuoss-Hsia equation, which provides the limiting molar conductance (LAMBDA0). This quantity is well fitted to the function proposed by Speedy and Angell (R. J. Speedy and C. A. Angell, J. Chem. Phys., 1976, 65, 851), LAMBDA0 = LAMBDA0(T/T(s) - 1)gamma, with a singular temperature T(s) for each binary mixture, where A0 and gamma are constants. Furthermore, the activation energy for the limiting equivalent conductivity has been evaluated on the basis of an Arrhenius equation and discussed in terms of the structural solvent-cosolvent complex adduct formation.
1993
- Conductivity of tetraphenylphosphonium bromide in 2-methoxyethanol - water
[Articolo su rivista]
F., Corradini; Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; G., Tosi
abstract
Thermodynamic properties from conductance data are reported for solutions of Ph4PBr in 2-methoxyethanol-water binary solvent mixtures, at 19 temperatures in the range -10 to +80-degrees-C and for six mixtures in the composition range 0.1865 less-than-or-equal-to X1 less-than-or-equal-to 1. The experimental conductivity values were analysed by the Fuoss-Hsia equation, and the salt was found to be associated to some extent in these mixtures. The experimental dissociation constant (K) of the ion pair for this electrolyte has been used to test some empirical equations representing the functions K = K(T), K = K(X1) and K = K(T, X1).
1993
- Dielectric properties of ethane-1,2-diol + 2-methoxyethanol + water liquid ternary mixtures
[Articolo su rivista]
F., Corradini; M., Malagoli; Marcheselli, Luigi; Marchetti, Andrea; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The dielectric properties of ethane-1,2-diol (1) + 2-methoxyethanol (2) + water (3) were measured in the range 30 less-than-or-equal-to t/degrees-C less-than-or-equal-to 50 and for 66 ternary mixtures covering the whole miscibility field (0 less-than-or-equal-to x1/x2/x3 less-than-or-equal-to 1). The epsilon values were analyzed by some empirical equations based on the pure-component properties for the ternaries studied. A comparison of the experimental and calculated data shows that the selected equations can be safely employed to predict the dependence of epsilon on the temperature and on the composition of the systems studied when binary and/or ternary experimental data are not available.
1993
- KINEMATIC VISCOSITIES OF BINARY-MIXTURES OF 1,2-ETHANEDIOL AND 2-METHOXYETHANOL AT DIFFERENT TEMPERATURES
[Articolo su rivista]
Marchetti, Andrea; Tagliazucchi, M; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Kinematic viscosities have been measured for 1,2-ethanediol, 2-methoxyethanol and nine binary mixtures thereof over the entire composition range and at 19 temperatures ranging from - 10 to 80-degrees-C. Several empirical relations (e.g. McAllister, Heric, Lobe, Grunberg-Nissan and polynomial equations) have been used in order to fit the experimental data and to correlate the binary mixture results with the kinematic viscosities of the pure components. All these approaches correlate the kinematic viscosity data well, while the adjustable parameters provide some useful information about the specific interactions between different molecules.
1993
- Kinematic viscosity studies of the binary ethane-1,2-diol / N,N-dimethylformamide solvent system at various temperatures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Kinematic viscosity data (nu) are presented for ethane-1,2-diol, for N,N-dimethylformamide and for nine binary mixtures in the - 10-degrees-C to 80-degrees-C temperature range. The experimental data were fitted by several empirical relations such as Grunberg-Nissan (1949), McAllister (1960), Heric (1966), Lobe (1973), Auslander (1964) and polynomial equations. Some considerations regarding the meaning of the obtained adjustment parameters are made. Furthermore, a new best fit equation is proposed and its validity has been compared to that of the other relations on the basis of the reproducibility of the experimental data.
1993
- Pollen Spectra and Lead Levels in Honey from the Urban Area of Modena (Northern Italy, 1991).
[Abstract in Rivista]
Mercuri, Anna Maria; L., Gavioli; F., Corradini; Marchetti, Andrea; C. A., Accorsi; Preti, Carlo
abstract
The use of honey for monitoring air pollution, specifically heavy metal pollution, in urban areas involves melissopalynological and chemical research. The honey's pollen spectra provide information on the plants from which honey-bees have collected nectar. We can thus recognize the area through which they have flown and evaluate the corresponding heavy metal levels.
1993
- THE RELATIVE PERMITTIVITY OF 1,2-DIMETHOXYETHANE WATER SOLVENT MIXTURES FROM -10 TO 80-DEGREES-C
[Articolo su rivista]
L., Marcheselli; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; G., Tosi
abstract
Relative permittivities (epsilon) and the excess property (epsilon(E)) for the binary mixtures formed by 1,2-dimethoxyethane with water have been measured at various temperatures in the range from -10 to +80-degrees-C. These mixtures have interesting properties for electroanalytical applications. Their study should help in understanding the phenomenology of cosolvency towards ionizable and inert solutes. The results of the epsilon(E) analysis are discussed in terms of the influence of interactions between the components, order and degree of packing in the mixtures, and any other structural effect which occurs in solution.
1993
- THE RELATIVE PERMITTIVITY OF 1,2-ETHANEDIOL PLUS 2-METHOXYETHANOL PLUS WATER TERNARY MIXTURES
[Articolo su rivista]
F., Casarini; L., Marcheselli; Marchetti, Andrea; Tassi, Lorenzo; G., Tosi
abstract
The relative permittivities epsilon for the ternary 1,2-ethanediol (component 1) + 2-methoxyethanol (2) + water (3) solvent system have been measured for 66 mixtures covering the whole mole fraction composition 0 less-than-or-equal-to X1/X2/X3 less-than-or-equal-to 1 range at -10, -5 and 0-degrees-C. The experimental data were used to test some empirical relations stating the dependence of epsilon = epsilon (X1, X2, X3). A comparison between the calculated and experimental data show that these equations can be usefully employed to predict epsilon values in correspondence of the experimental data gaps.
1993
- Viscosities of 1,2-ethanediol - 2-methoxyethanol solvent mixtures at various temperatures
[Articolo su rivista]
F., Corradini; Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; G., Tosi
abstract
Viscosities were measured for binary solvent mixtures of 1,2-ethanediol-2-methoxyethanol at 19 temperatures ranging from -10 to 80 degrees C. Several different equations, such as those of Arrhenius, Waterton, and Williams et al., have been applied in order to establish the best regression fit for eta as a function of temperature. For this binary solvent system, the viscometric properties are continuous but not a linear function of the mixture composition. The deviations of the excess viscosities from ideality were found to be useful in detecting the formation of solvent-cosolvent complex species and to evaluate their stoichiometrical composition.
1993
- Viscosity data and viscous flow thermodynamics of 2-methoxyethanol + water binary mixtures
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Kinematic viscosities (v) have been measured for pure 2-methoxyethanol, pure water, and nine of their mixtures over the entire composition range and, where possible, at 19 temperatures ranging from -10 to +80-degrees-C. The above property was fitted by empirical equations stating its dependence on temperature (T) and mole fraction (XI) of the mixtures. The experimental data for the binary mixtures were used to test the validity of mixing rules at different temperatures.
1992
- CRYSTAL AND MOLECULAR-STRUCTURE OF TETRAMETHYLAMMONIUM PICRATE
[Articolo su rivista]
Antolini, Luciano; Marchetti, Andrea; Preti, Carlo; Tagliazucchi, M.
abstract
The synthesis and crystal and molecular structure of the tetramethylammonium picrate [C4H12N+C6H2N3O7-] is reported. It belongs to the triclinic space group P1BAR with a = 7.300(3), b = 9.797(2), c = 10.841(3) angstrom, alpha = 64.70(2), beta = 88.60(3), gamma = 79.55(2)-degrees and Z = 2. The structure was refined to a final R value equal to 0.046 (R(w) = 0.053) for 1817 unique reflections. The crystal packing consists of parallel layers of anions interacting through electrostatic and short van der Waals contacts with neighboring cations. Vibrational spectra have been recorded and discussed.
1992
- Dissociation constants of picric acid in mixtures of N,N-dimethylformamide + ethane-1,2-diol
[Articolo su rivista]
F., Corradini; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The acid dissociation constants of 2,4,6-trinitrophenol (picric acid) were determined in N,N-dimethylformamide and ethane-1,2-diol from -10 to +80-degrees-C and in two N,N-dimethylformamide + ethane-1,2-diol mixtures from +20 to +80-degrees-C using the conductometric method. The experimental conductivity data were analyzed by means of the Fuoss-Hsla equation, and the dissociation constants were fitted by the integrated Van't Hoff equation.
1992
- N,N-DIMETHYLFORMAMIDE-2-METHOXYETHANOL SOLVENT SYSTEM - DENSITIES AND EXCESS MOLAR VOLUMES AT VARIOUS TEMPERATURES
[Articolo su rivista]
Marcheselli, Luigi; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Densities (rho) have been measured for N,N-dimethylformamide (1), 2-methoxyethanol (2), and for nine binary mixtures covering the whole miscibility field (0 less-than-or-equal-to X1 less-than-or-equal-to 1) in the temperature range - 10- + 80-degrees-C. The experimental data were used to test some empirical equations of the type rho = rho(t), rho = rho(X1) and rho = rho(t, X1). Furthermore, the excess volumes (V(E)) for these binaries have been examined and discussed at all the investigated temperatures in terms of the influence of interactions between unlike molecules. The V(E) vs. X1 plots suggest the presence of some stable adducts, having N,N-dimethylformamide: 2-methoxyethanol stoichiometric ratios of 1 : 2 and 1 : 1 depending on the temperature.
1992
- SYNTHESIS AND CHARACTERIZATION OF LANTHANIDE COMPLEXES - LANTHANUM(III), CERIUM(III) AND EUROPIUM(III) DERIVATIVES WITH PARA-SUBSTITUTED AND META-SUBSTITUTED BENZENESELENINIC ACIDS
[Articolo su rivista]
G., Graziosi; Marchetti, Andrea; Preti, Carlo; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
New complexes of lanthanum(III), cerium(III) and europium(III) with para- and meta-substituted benzeneseleninic acids of the type XC6H4SeO2H (X = H, m-Cl, p-Br, p-Me) are reported. The compounds Ln(XC6H4SeO2)3, Ln(XC6H4SeO2)2Cl, Ln(XC6H4SeO2)Cl2 and Ln2(XC6H4SeO2)3Cl3, where Ln denotes trivalent La, Ce, and Eu, have been studied using spectroscopic techniques (ir, far-ir and electronic spectra), magnetic susceptibility, thermogravimetric and conductivity measurements. The electronic spectra of the 1 : 3 derivatives have been analysed and spectral parameters are calculated and discussed for the europium complexes. The ir data point to a seleninato-O,O' coordination for all the complexes; in particular, the presence of three SeO bands with irreducible representation A 2 + 2E in the ir spectra of the tris derivatives suggests an octahedral configuration with D 3 symmetry. All the halo derivatives are polymeric and octahedral in nature with bridging halide atoms. The magnetic moment values lie in the expected ranges and show very little deviation from Van Vleck values.
1992
- Static, Microwave, Infrared, and Visible Permittivity Related to Chemical Structure:N-Methylacetamide, N,N-Dimethylacetamide, and Their Mixtures in CCI, at 32 C
[Articolo su rivista]
Paul, Firman; Edward M., Eyring; Meizhen, Xu; Marchetti, Andrea; Sergio, Petrucci
abstract
Static dielectric permittivities, eo, and visible refractive indices, nI, (at the sodium doublet X = 589.3 nm) are reported forN-methylacetamide (NMA), N,N-dimethylacetamide (DMA), their mixtures with CCl, over a broad concentration range,and NMA-DMA mixtures over a broad range of concentrations at 32 OC. UHF and microwave complex permittivities from0.3 to 90 GHz and far-infrared refractive indices at F = 130 and 3 = 380 cm-' for NMA and their mixtures with CC4 andat F = 130 cm-' for DMA-CC14 mixtures up to 1 M DMA at 32 OC are also reported. Dramatic differences between NMAand DMA in both the static permittivities and relaxation times (for both pure liquids and their mixtures in CCl.,) are attributedto chain formation through H bonding for the monosubstituted amides. DMA acts as a kind of "chain-terminator" whenadded to NMA. The difference in behavior between the two liquids disappears in the cases of infrared permittivities andvisible nD2 values.
1992
- The Relative Permittivity of N,N-Dimethylformamide/1,2-Dimethoxyethane Binary Mixtures from -10 to 40 C
[Articolo su rivista]
Goldoni, Gianni; Marcheselli, Luigi; Marchetti, Andrea; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Binary solutions of N,N-dimethylformamide and 1,2-dimethoxyethane have been investigated by means of dielectric measurements at temperatures ranging from −10 to +40°C, and for nine mixtures covering the whole miscibility field expressed by the mole fraction of one component (0≤X1≤1). The experimental data were used to study the dependence of ɛ on T and X1, of the type ɛ = ɛ(T), ɛ = ɛ(X1), and ɛ = ɛ(T,X1). Further, the excess mixing function ɛE has been evaluated in order to identify particular patterns of interaction between unlike molecules and any other factor that could modify such patterns. The minimum in the ɛE vs. composition plots suggests the formation of an adduct of stoichiometric ratio DMF∶DME=1∶1 at all the investigated temperatures.
1992
- Titrimetric behaviour of picric acid in mixed 2-methoxyethanol/water solvent system
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The titrimetric behaviour of picric acid in pure 2-methoxyethanol, in pure water and in many of their binary mixtures has been investigated by using the conductometric method and 1,1,3,3-tetramethylguanidine as titrant base. The study has been carried out working at 0, 25, 50 and 75-degrees-C and the effects of temperature and composition of the solvent mixture on the shape of the curves and on the accuracy of the analytical recovery have been pointed out. Previous observations on the hypothetical existence of a particular ''limiting mixture'' which separates the solvent system under study into two groups (0 less-than-or-equal-to X(water) < ''limiting mixture' and ''limiting mixture'' < X(water) less-than-or-equal-to 1, where X represents the mole fraction) have been confirmed and a stoichiometric composition for such a mixture, which depends on temperature, has been suggested.
1992
- Viscosities and activation energies of viscous flow of the 1,2-ethanediol / N,N-dimethylformamide binary solvent system
[Articolo su rivista]
F., Corradini; L., Marcheselli; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; G., Tosi
abstract
Densities (rho) and absolute viscosities (eta) of pure 1,2-ethanediol, NN-dimethylformamide and of their nine mixtures were determined at nineteen temperatures ranging between -10 and +80-degrees-C. The above properties were fitted by empirical equations stating their dependence on temperature and composition of the mixtures. The extrathermodynamic excess functions, such as the excess rheochor [R(E)] and the excess Gibbs energy of activation of viscous flow DELTA-G(E), have been studied. The trend of [R(E)] vs. composition of the mixtures shows negative deviations from ideality, indicating extensive molecular interactions between the components of the binary solvent system. Furthermore, activation enthalpies and entropies for viscous flow have been obtained and their variations with composition have also been discussed.
1991
- CRYSTAL-STRUCTURE OF N,N'-DIPHENYL-GUANIDINIUM M-CHLOROBENZENESELENINATE
[Articolo su rivista]
Antolini, Luciano; Marchetti, Andrea; Preti, Carlo; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The synthesis, and crystal and molecular structure of N,N'-diphenylguanidinium m-chlorobenzeneseleninate (C19H18ClN3O2Se), M(r) 434.78, are reported. The crystal lattice of the compound belongs to the monoclinic space group P2(1)/c with a 7.277(1), b 12-793(2), c 20.013(4) angstrom, beta-94.733(12)-degrees, V 1859.8 angstrom3, Z 4, D(obs) 1. 53 (by flotation), D(calc) 1.555 g cm-3, lambda(Mo K-alpha) 0.71069 angstrom, mu-21.0 cm-1, F(000) 880, T 293 K, R 0.057 and R(w) 0.059 for 1745 unique observed reflections with I > 2.0-sigma(I). The crystal packing consists of parallel layers of anions intercalated with cations interacting through electrostatic contacts. Vibrational spectra have been also recorded, and are discussed.
1991
- Density and excess molar volumes of the 1,2-ethanediol + 2-methoxyethanol solvent system at various temperatures
[Articolo su rivista]
Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Densities are reported for the binary mixture 1,2-ethanediol + 2-methoxyethanol in the whole composition range at 19 temperatures between -10 and +80-degrees-C. The excess molar volumes, V(E), calculated from the density values, are negative at all concentrations and become more negative with increasing temperature.
1991
- Dissociation equilibria of picric acid in the binary N,N-dimethylformamide / 2-methoxyethanol solvent system
[Articolo su rivista]
Marchetti, Andrea; Preti, Carlo; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Three empirical equations are proposed to fit the experimental values of the dissociation constant for picric acid, chosen as guide-solute working in the N,N-dimethylformamide/2-methoxyethanol solvent system. The work was performed operating at 19 temperatures ranging from - 10 to + 80-degrees-C in the pure solvents and in their nine mixtures, identified by the mole fraction (X) of one component. This empirical treatment, which describes the dependence of the dissociation constant on temperature and composition of the solvent mixture, is represented by functions of the type K = K(T), K = K(X), and K = K(T, X). The K = K(T, X) equation in its complete form is composed of 20 terms, some of which can be eliminated because of small statistical weight; the number and type of these terms vary on passing from one solvent system to another and the best-fitting form is suggested. A comparison among various K = K(T, X) equations proposed in the present and in previous works has been made.
1991
- Ethane-1,2-diol - 2-methoxyethanol solvent system. Dependence of the relative permittivity and refractive index on the temperature and composition of the binary mixture
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The extrathermodynamic parameters, relative permittivity (epsilon-r) and refractive index (n), have been measured for ethane-1,2-diol-2-methoxyethanol binary mixtures over the entire composition range, at various temperatures ranging between - 10 and 80-degrees-C. For this system, as far as for many solvent-cosolvent systems which are useful for analytical and electrochemical applications, the properties cited above are continuous but not linear functions of the binary composition. Various equations have been applied in order to establish the best regression models for the relationship y = f(X), where X is the composition of the mixture. On the whole, minima occurred in the excess function (epsilon-E), showing the existence of various solvent-cosolvent complexes of different stoichiometric ratios (2:1, 1:1 or 1:2) and of different thermostabilities, which may be interpreted in terms of moderate interactions such as dipolarity, polarizability and hydrogen bonding between the mixed solvents. Among the above complexes, the ethane-1,2-diol-2-methoxyethanol 1:2 adduct is suggested to be the true 'limiting mixture', on the borderline between the types of behaviour typical of the two pure solvents. Furthermore, empirical patterns in the refractive index were used to scrutinize the most important mixing rules in order to determine the properties of the mixture on the basis of those of its pure components.
1991
- Infrared and microwave dielectric relaxation of benzonitrile, acetonitrile and their mixtures with carbon tetrachloride at 25 C
[Articolo su rivista]
P., Firman; Marchetti, Andrea; M., Xu; Edward M., Eyring; S., Petrucci
abstract
Infrared refractive indices at B N 300 cm-I (f = 9OOO GHz) and P N 400 cm-I (f = 12 OOO GHz) and complex permitthitiese* = t' - Jd' at 3 = 300 cm-' and Y Y 400 cm-I for acetonitrile and acetonitrile-carbon tetrachloride as well as benzonitrileand benzonitrile-carbon tetrachloride mixtures at B N 125 cm-' (3750 GHz) at 25 OC are reported. Microwave complexpermittivities e*, in the frequency range -0.4-90 GHz for the same systems at 25 O C , are also reported. Visible refractiveindices at X = 589.3 nm (the sodium D line) for benzonitrile and benzonitrile-xrbon tetrachloride mixtures and for acetonitrileand acetonitrile-carbon tetrachloride mixtures and static dielectric permittivities for the same systems at 25 OC are reported.The observed dielectric relaxation processes at microwave frequencies up to 13.8 GHz for pure benzonitrile and up to 80GHz for acetonitrile can be described by a single Debye relaxation function, using a parameter e,. This value is larger thanthe figure for nIR2 at P = 125 cm-I for pure benzonitrile. For pure benzonitrile, an almost complete profile of d = d wwavenumber 3 has been determined up to the visible. For the mixtures, a single Debye relaxation function can describe themicrowave dielectric data by using a parameter e,. The latter becomes practically equal to nn2, within experimental error,for mixtures of composition XwsN I 0.10 and XCH,CIN 0 .05, respectively. Potential applications of t, (or nIR2)d ata inevaluating the longitudinal relaxation times rL and the short-range structural relaxation time rG in femtosecond-picdmolecular dynamics studies of solvation and the need for a better understanding of the dielectric properties of mixed liquidsin the development of supercapacitors are both noted.
1991
- The N,N-dimethylformamide + ethane-1,2-diol solvent system. Dielectric constant, refractive index, and related properties at various temperatures
[Articolo su rivista]
Marchetti, Andrea; Preti, Carlo; M., Tagliazucchi; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Dielectric constant (epsilon) and refractive indexes (n) were measured for pure N,N-dimethylformamide, ethane-1,2-diol, and their six mixtures over the entire composition range and, where possible, at nineteen selected temperatures ranging between -10 and +80-degrees-C. The above properties were fitted by empirical equations stating their dependence on temperature (T) and mole fraction (x1) of the mixture. The refractive indexes of the binary mixtures were used to test the validity of mixing rules at different temperatures.
1991
- The N,N-dimethylformamide / ethane-1,2-diol solvent system. Density, viscosity and excess molar volume at various temperatures
[Articolo su rivista]
Marchetti, Andrea; C., Preti; M., Tagliazucchi; Tassi, Lorenzo; G., Tosi
abstract
Density (rho), kinematic viscosity (nu), and absolute viscosity (eta) are presented for mixtures of ethane-1,2-diol and N,N-dimethylformamide from -10 to +80-degrees-C. The above properties were fitted by empirical equations stating their dependence on temperature and mole fraction of the mixture. Furthermore, some considerations regarding the meaning of the obtained adjustment parameters are made. The excess functions, such as molar volumes V(E), have been derived. The trends of V(E) data vs mole fraction of the mixtures have exhibited markedly negative deviations from ideality, indicating extensive molecular interactions between the components of the binary solvent system.
1990
- Ionization and Dissociation of Weak Electrolytes. An Initial Approach to Kd and Ki Evaluation.
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The experimental dissociation constant K of weak electrolytes may be consldered as derlved from dlfferent contributions due to the Ionization, K,,and dlssociation, Kd,equlllbrla, respec- tively. AsimplemethodforK,andKdevaluatlonisherein proposed, startlng from experimental K data, obtained by the conductometric method, for plcrlc acld in a set of binary solventsystemmixturesattemperaturesrangingfrom-10 to +80 O C . The correlatlonsbetweenK,and Tand betweenK, and Tare moreover suggested on the basis of a general ex- pression derlved from the Integrated Van’t Hoff equation.
1989
- An Approach to the Problem of the Dependence of the Dissociation Constant of Weak Electrolytes on the Temperature and the Solvent Composition in the Ethane-1,2-diol / 2-Methoxyethanol Solvent System.
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; Preti, Carlo; Tassi, Lorenzo; Tosi, Giuseppe
abstract
This empirical approach to clarify the problem of the dependence of the dissociation constants of weak electrolytes on temperature and composition of mixed solvents systems (X) is applied to the dissociation constant of picric acid in ethane-1,2-diol, in 2-methoxyethanol and in their binary mixtures. The data utilized here are those of previous work (recalculated by means of the more accurate Fuoss–Hsia equation) integrated by the experimental data relative to three new mixtures. Two equations of the dependence of K on T and of K on X, respectively, are suggested and good accordance between experimental and calculated values is shown. Starting from the two above-mentioned equations, general empirical equations for the surface K(T, X) are proposed; the average difference between calculated and experimental K values is ca. 8 %. A three-dimensional plot of the function K=K(T, X) is presented. The proposed empirical models are compared to that obtained for the previously studied ethane-1,2-diol–water solvent system and advantages and limitations of the models are discussed.
1989
- Conductometric Titration of Poliprotic Acids in non Aqueous Mixed Solvents. Effects of Temperature and Composition of the Solvent Mixture.
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; Preti, Carlo; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The effects of temperature and composltlon of the solvent mixtures on the shape and on the analytical recoveries of conductometric tltratlons of polyprotlc aclds were studled for the solvent system 2-methoxyethanol/ethane-1,2-diol operating at -10, 25, 50, and 75 °C. The experimental evidence indicates that the N- or chair-shape of the tltratlon curves depends on the solvent physicochemical propertles, on the temperature, and on the acld solute to be tltrated; in particular the Influence of the distance between the carboxylic groups Is discussed. Titrations performed In 2-methoxyethanoi are associated in general wlth N-shaped curves, which however turn to chalr-shaped as the temperature Increases. Ethane-1,2-diol always produces chair-shaped curves as a consequenceof its more dlssoclating ability toward the tltratlonformed adducts. The study of the tltrations of phthalic acld In some mixtures of the above solvents exhibited behaviors consistent wlth previous observations regarding the exlstence of a partlcuiar “limiting mlxture” whlch separates the solvent system under study Into two well-defined groups (0 Ix . ~< “~limiting mixture” and “limiting mixture”
1989
- Ionic Equilibria of Picric Acid in Mixed Anphiprotic Solvents.The 2-Methoxyethanol/Water Solvent System.
[Articolo su rivista]
Marchetti, Andrea; E., Picchioni; Tassi, Lorenzo; Tosi, Giuseppe
abstract
Picric acld Is the gulde solute used In our studies In order to verify the applicability of an emplrikal treatment that descrlbes the dependence of the dlssoclatlon constant on temperature and composltlon of the solvent mlxture ( x Is mole fractlon).The 2-methoxyethano/water solvent system has been employed In thls work operatlng at 19 temperatures ranging from -10 to +80 °C; by use of the conductometric method the dissociation constant values of plcrlc acld have been evaluated by the Fuoss-Hsla equation. The data have been fltted by three emplrlcal equations that represent the functlons K = K(T), K = K ( x ) , and K = K(T,x). The K = K(T,x) equatlon In Its complete form Is composed of 20 terms, someof whkh can be elhnlnated because of small statistkal weigt; the number and type of these terms vary on passlng from one solvent system to another, and the best-flttlng form, which In thls case represents 13 terms, Is suggested. The posslblllty of extrapolatlng K values of plcrk acM In a pure water solutlon Is lnvestlgated and compared wlth similar previous calculatlons.
1988
- The Ethane-1,2-diol/Water Solvent System. The Dependence of the Dissociation Constant of Picric Acid on the Temperature and Composition of the Solvent Mixture.
[Articolo su rivista]
Franchini, Giancarlo; Marchetti, Andrea; Tassi, Lorenzo; Tosi, Giuseppe
abstract
The dissociation constants of 2,4,6-trinitrophenol (picric acid) in a set of ethane-1,2-diol–water mixtures have been determined by the conductometric method at temperatures ranging from –10 to 80 °C. The experimental k values exhibit a regular trend, with a relative maximum in the investigated temperature range for all the binary solvent systems, and they are well fitted by an equation of the type ln K=a0+a1T+a2/T+a3 ln T. In order to verify the reliability of Kmax values, a series of correlations was made, on the basis of the above equation, of Harned's theory and of a pKvs. 1/ε plot; all the methods provide results consistent with each other. Furthermore, two empirical equations for the functions K=K(χ) and K=K(T,χ) are proposed in order to try to predict the K values of the studied solute over the whole variation of the investigated T and χ. Both these model equations allow us to extrapolate the K values of picric acid in pure water solution, in which conductometric and potentiometric methods are unable to give consistent values.