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Caterina DURANTE
Ricercatore t.d. art. 24 c. 3 lett. B
Dipartimento di Scienze Chimiche e Geologiche - Sede Dipartimento di Scienze Chimiche e Geologiche
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Pubblicazioni
2023
- A Feasibility Study towards the On-Line Quality Assessment of Pesto Sauce Production by NIR and Chemometrics
[Articolo su rivista]
Tanzilli, Daniele; D'Alessandro, Alessandro; Tamelli, Samuele; Durante, Caterina; Cocchi, Marina; Strani, Lorenzo
abstract
The food industry needs tools to improve the efficiency of their production processes by minimizing waste, detecting timely potential process issues, as well as reducing the efforts and workforce devoted to laboratory analysis while, at the same time, maintaining high-quality standards of products. This can be achieved by developing on-line monitoring systems and models. The present work presents a feasibility study toward establishing the on-line monitoring of a pesto sauce production process by means of NIR spectroscopy and chemometric tools. The spectra of an intermediate product were acquired on-line and continuously by a NIR probe installed directly on the process line. Principal Component Analysis (PCA) was used both to perform an exploratory data analysis and to build Multivariate Statistical Process Control (MSPC) charts. Moreover, Partial Least Squares (PLS) regression was employed to compute real time prediction models for two different pesto quality parameters, namely, consistency and total lipids content. PCA highlighted some differences related to the origin of basil plants, the main pesto ingredient, such as plant age and supplier. MSPC charts were able to detect production stops/restarts. Finally, it was possible to obtain a rough estimation of the quality of some properties in the early production stage through PLS.
2023
- An analytical approach based on excitation-emission fluorescence spectroscopy and chemometrics for the screening of prostate cancer through urine analysis: A proof–of–concept study
[Articolo su rivista]
Mustorgi, Eleonora; Durante, Caterina; Malegori, Cristina; Greco, Piergiorgio; Bartoletti, Riccardo; Cocchi, Marina; Casale, Monica
abstract
In the present feasibility study, excitation-emission fluorescence spectroscopy has been investigated, as a rapid
and accurate analytical method for the development of a tentative model for the early screening of prostate
cancer directly through urine analysis in order to provide reliable results while improving patient compliance.
Sixty-nine urine samples (46 samples from patients with histologically proven prostate cancer and 23 from
healthy donors) were provided, by the University of Pisa, Urology Unit. The excitation-emission fluorescence
measurements were performed on centrifugated urine samples at room temperature on a Perkin-Elmer LS55B
luminescence spectrometer and the corresponding data array was analysed with parallel factor analysis
(PARAFAC).
From a synergistic analysis of the obtained results, four main fluorophores, corresponding to four selected
PARAFAC factors, were recognizable in the urine excitation-emission matrices (EEMs) and the respective species
could be potential markers in the differentiation among healthy and cancer samples. PARAFAC results, in terms
of extracted scores, coupled with discriminant algorithms, allowed to develop a first attempt of healthy/cancer
discrimination model. The chemometrics models show promising correlation between some of the depicted
fluorophores and the disease state. However, considering the limited cohort (not only in terms of number but also
of representativeness), this study must be considered as a proof of concept; a more sound and statistically
relevant sampling must be performed in order to consider the confounding factors in the cohort treated and to
develop an analytical approach applicable in real scenarios.
2023
- Exploring the Effect of Different Storage Conditions on the Aroma Profile of Bread by Using Arrow-SPME GC-MS and Chemometrics
[Articolo su rivista]
Pellacani, Samuele; Cocchi, Marina; Durante, Caterina; Strani, Lorenzo
abstract
: In the present feasibility study, SPME Arrow-GC-MS method coupled with chemometric techniques, was used for investigating the impact of two different storage conditions, namely freezing and refrigeration, on volatile organic compounds (VOCs) of different commercial breads. The SPME Arrow technology was used as it is a novel extraction technique, able to address issues arising with traditional SPME fibers. Furthermore, the raw chromatographic signals were analysed by means of a PARAFAC2-based deconvolution and identification system (PARADISe approach). The use of PARADISe approach allowed for an efficient and rapid putative identification of 38 volatile organic compounds, including alcohols, esters, carboxylic acids, ketones, and aldehydes. Additionally, Principal Component Analysis, applied on the areas of the resolved compounds, was used to investigate the effects of storage conditions on the aroma profile of bread. The results revealed that the VOC profile of fresh bread is more similar to the one of bread stored in the fridge. Furthermore, there was a clear loss of aroma intensity in frozen samples, which could be explained by phenomena related to different starch retrogradation that occurs during freezing and refrigeration. However, considering the limited number of investigated samples, this study must be considered as a proof of concept; a more statistically representative sampling and further examinations of other properties, such as bread texture, need to be performed to better understand whether samples destined for eventual analysis should be frozen or refrigerated.
2023
- Near Infrared and UV-Visible Spectroscopy Coupled with Chemometrics for the Characterization of Flours from Different Starch Origins
[Articolo su rivista]
Pellacani, Samuele; Borsari, Marco; Cocchi, Marina; D'Alessandro, Alessandro; Durante, Caterina; Farioli, Giulia; Strani, 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
- Tracing the identity of Parmigiano Reggiano “Prodotto di Montagna - Progetto Territorio” cheese using NMR spectroscopy and multivariate data analysis
[Articolo su rivista]
Cavallini, N.; Strani, L.; Becchi, P. P.; Pizzamiglio, V.; Michelini, S.; Savorani, F.; Cocchi, M.; Durante, C.
abstract
Background
Nuclear magnetic resonance (NMR) spectroscopy is one of the well-established tools for food metabolomic analysis, as it proved to be very effective in authenticity and quality control of dairy products, as well as to follow product evolution during processing and storage. The analytical assessment of the EU mountain denomination label, specifically for Parmigiano Reggiano "Prodotto di Montagna - Progetto Territorio" (Mountain-CQ) cheese, has received limited attention. Although it was established in 2012 the EU mountain denomination label has not been much studied from an analytical point of view. Nonetheless, tracing a specific profile for the mountain products is essential to support the value chain of this specialty.
Results
The aim of the study was to produce an identity profile for Parmigiano Reggiano “Prodotto di Montagna - Progetto Territorio” (Mountain-CQ) cheese, and to differentiate it from Parmigiano Reggiano PDO samples (conventional-PDO) using 1H NMR spectroscopy coupled with multivariate data analysis. Three different approaches were applied and compared. First, the spectra-as-such were analysed after proper preprocessing. For the other two approaches, Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) was used for signals resolution and features extraction, either individually on manually-defined spectral intervals or by reapplying MCR-ALS on the whole spectra with selectivity constraints using the reconstructed “pure profiles” as initial estimates and targets. All approaches provided comparable information regarding the samples’ distribution, as in all three cases the separation between the two product categories conventional-PDO and Mountain-CQ could be highlighted. Moreover, a novel MATLAB toolbox for features extraction via MCR-ALS was developed and used in synergy with the Chenomx library, allowing for a putative identification of the selected features.
Significance
A first identity profile for Parmigiano Reggiano “Prodotto di Montagna - Progetto Territorio” obtained by interpreting the metabolites signals in NMR spectroscopy was obtained. Our workflow and toolbox for generating the features dataset allows a more straightforward interpretation of the results, to overcome the limitations due to dimensionality and to peaks overlapping, but also to include the signals assignment and matching since the early stages of the data processing and analysis.
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
- 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
- Fast GC E-Nose and Chemometrics for the Rapid Assessment of Basil Aroma
[Articolo su rivista]
Strani, Lorenzo; D'Alessandro, Alessandro; Ballestrieri, Daniele; Durante, Caterina; Cocchi, Marina
abstract
The aim of this work is to assess the potentialities of the synergistic combination of an ultra-fast chromatography-based electronic nose as a fingerprinting technique and multivariate data analysis in the context of food quality control and to investigate the influence of some factors, i.e., basil variety, cut, and year of crop, in the final aroma of the samples. A low = level data fusion approach coupled with Principal Component Analysis (PCA) and ANOVA—Simultaneous Component Analysis (ASCA) was used in order to analyze the chromatographic signals acquired with two different columns (MXT-5 and MXT-1701). While the PCA analysis results highlighted the peculiarity of some basil varieties, differing either by a higher concentration of some of the detected chemical compounds or by the presence of different compounds, the ASCA analysis pointed out that variety and year are the most relevant effects, and also confirmed the results of previous investigations.
2022
- Rapid Classification and Recognition Method of the Species and Chemotypes of Essential Oils by ATR-FTIR Spectroscopy Coupled with Chemometrics
[Articolo su rivista]
Truzzi, E.; Durante, C.; Bertelli, D.; Catellani, B.; Pellacani, S.; Benvenuti, S.
abstract
In the present work, the applicability of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, coupled with chemometric tools in recognizing essential oils (EOs) for routine control, was evaluated. EOs belonging to Mentha, Cymbopogon, and Lavandula families and to S. rosmarinus and T. vulgaris species were analyzed, and the performance of several untargeted approaches, based on the synergistic combination of ATR-FTIR and Partial Least Squares Discriminant Analysis (PLS-DA), was tested to classify the species and chemotypes. Different spectra pre-processing methods were employed, and the robustness of the built models was tested by means of a Receiver Operating Characteristic (ROC) curve and random permutations test. The application of these approaches revealed fruitful results in terms of sensitivity and specificity, highlighting the potentiality of ATR-FTIR and chemometrics techniques to be used as a sensitive, cost-effective, and rapid tool to differentiate EO samples according to their species and chemotype.
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
- Characterization of Basil Volatile Fraction and Study of its Agronomic Variation by ASCA
[Articolo su rivista]
D'Alessandro, Alessandro; Ballestrieri, Daniele; Strani, Lorenzo; Cocchi, Marina; Durante, Caterina
abstract
Basil is a plant known worldwide for its culinary and health attributes. It counts more
than a hundred and fifty species and many more chemo-types due to its easy cross-breeds. Each species and each chemo-type have a typical aroma pattern and selecting the proper one is crucial for the food industry. Twelve basil varieties have been studied over three years (2018–2020), as have four different cuts. To characterize the aroma profile, nine typical basil flavour molecules have been selected using a gas chromatography–mass spectrometry coupled with an olfactometer (GC–MS/O). The concentrations of the nine selected molecules were measured by an ultra-fast CG e-nose and Principal Component Analysis (PCA) was applied to detect possible differences among the samples.
The PCA results highlighted differences between harvesting years, mainly for 2018, whereas no observable clusters were found concerning varieties and cuts, probably due to the combined effects of the investigated factors. For this reason, the ANOVA Simultaneous Component Analysis (ASCA) methodology was applied on a balanced a posteriori designed dataset. All the considered factors and interactions were statistically significant (p < 0.05) in explaining differences between the basil aroma profiles, with more relevant effects of variety and year.
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
- Multi Way Classification
[Capitolo/Saggio]
Cocchi, Marina; Li Vigni, Mario; Durante, Caterina
abstract
In this Chapter, the state-of-the-art approaches for the classification of multi-way data is presented and discussed. The theoretical basis and applicative guidelines for multilinear (or multi-way) Partial Least Squares Discriminant Analysis (NPLS-DA) and Multi-way Soft Independent Modelling of Class Analogy (NSIMCA) are detailed. Furthermore, two-dimensional linear discriminant analysis (2DLDA) and a proposal for truly multilinear discriminant analysis are illustrated. The truly multi-way methods are compared to unfolding and feature extraction followed by bilinear classification. Practical hints are depicted through discussion of a case of study.
2020
- Preliminary Assessment of Parmigiano Reggiano Authenticity by Handheld Raman Spectroscopy
[Articolo su rivista]
Li Vigni, M.; Durante, C.; Michelini, S.; Nocetti, M.; Cocchi, M.
abstract
Raman spectroscopy, and handheld spectrometers in particular, are gaining increasing attention in food quality control as a fast, portable, non-destructive technique. Furthermore, this technology also allows for measuring the intact sample through the packaging and, with respect to near infrared spectroscopy, it is not affected by the water content of the samples. In this work, we evaluate the potential of the methodology to model, by multivariate data analysis, the authenticity of Parmigiano Reggiano cheese, which is one of the most well-known and appreciated hard cheeses worldwide, with protected denomination of origin (PDO). On the other hand, it is also highly subject to counterfeiting. In particular, it is critical to assess the authenticity of grated cheese, to which, under strictly specified conditions, the PDO is extended. To this aim, it would be highly valuable to develop an authenticity model based on a fast, non-destructive technique. In this work, we present preliminary results obtained by a handheld Raman spectrometer and class-modeling (Soft Independent Modeling of Class Analogy, SIMCA), which are extremely promising, showing sensitivity and specificity of 100% for the test set. Moreover, another salient issue, namely the percentage of rind in grated cheese, was addressed by developing a multivariate calibration model based on Raman spectra. It was possible to obtain a prediction error around 5%, with 18% being the maximum content allowed by the production protocol.
2018
- Aesthetic compatibility assessment of consolidants for wall paintings by means of multivariate analysis of colorimetric data
[Articolo su rivista]
Becherini, F.; Durante, C.; Bourguignon, E.; Li Vigni, M.; Detalle, V.; Bernardi, A.; Tomasin, P.
abstract
Background and methods: Wall paintings and architectural surfaces in outdoor environments are exposed to several physical, chemical and biological agents, hence they are often treated with different products to prevent or slow down their deterioration. Among the factors that have to be taken into account in the selection of the most suitable treatment for decorated surfaces, the aesthetic compatibility with the substrate is of great importance in the cultural heritage field; minimizing colour variation after treatment application is a crucial issue in particular for painted surfaces. In the framework of the European Project Nanomatch the color variation induced on wall painting mock-ups by the two innovative consolidants (calcium alkoxides) developed was evaluated using colorimetry in comparison with two traditional products. In this work these innovative consolidants have been also tested in combination with two commercial biocides and the results of colorimetric measurements discussed. Moreover, as the univariate approach didn't allow to draw clear conclusions on the relation between the different sources of data variability, multivariate analysis was performed on colorimetric data. Results: Principal Component Analysis and multi-way Parallel Factor Analysis (PARAFAC) were successfully applied to colorimetric data to investigate the short-term effects of the application of different consolidants on wall painting surfaces, making it possible to study at the same time the different sources of data variability, i.e. treatments, painting techniques, pigments. Finally, a ranking list of the treatments under study in terms of colour variation induced on the surface was established, in function of the painting technique and pigment, taking also in consideration the combination consolidant/biocide. In particular, given the true multi-way nature of the data, PARAFAC model turned out to be extremely useful in the study of the dependence of colour variation on pigments, a critical issue for painted surfaces, that was not clear using univariate approach. Conclusions: Multivariate approach to colorimetric data and especially 3-way PARAFAC method resulted a powerful technique to evaluate in short-term the color compatibility of consolidants for wall paintings, improving data interpretation and visualization, and thus outperforming the univariate statistical analysis.
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.
2018
- LC-HRMS for characterizing durum wheat pasta production variability and consumer overall liking
[Articolo su rivista]
Lambertini, F.; Cavanna, D.; Catellani, D.; Vigni, M. L.; Durante, C.; D'Alessandro, A.; Suman, M.
abstract
Semolina pasta represents one of the most important dishes in Italian cuisine worldwide. Italy is the leader in its production and, recently, the worldwide diffusion of its production has begun to grow tremendously. The perceived quality of a food product, such as pasta, is a key feature that allows a company to increase and maintain the competitive advantage of a specific brand. The overall flavor perception of the consumer, therefore, has become as important as other key quality factors such as texture and color; thus, the food industry needs to meet consumer expectations and needs the tools to objectively “measure” the quality of food products. Untargeted fingerprinting by means of coupling LC with high-resolution MS (HRMS) has been well received within the analytical community, and different studies exploiting this approach for the characterization of high-value food products have recently been reported in the literature. In the present work, a tentative application of the sensomics approach to cluster analysis of semolina pasta obtained using different production conditions was developed to objectively define target molecules that correlate with consumer overall liking of an industrial standard product. Principal component analysis of chemical and physical testing, GC-MS, LC-HRMS, and sensory data were performed with the aim of identifying the main parameters to discern similarities and differences among samples and clustering them according to these features. The correlation between analytical data and compounds related to sensory data was further investigated, and lastly, a partial least-squares regression model for the prediction of consumer overall liking was reported.
2017
- Chemometrics, Bioinformatics
[Capitolo/Saggio]
Durante, Caterina; LI VIGNI, Mario; Cocchi, Marina
abstract
The need to consider variability due to raw materials, seasonality, agricultural practices, and food processing, that are aspects which all play a role in authenticity tasks, justifies the need for chemometrics methods. This chapter presents a few basic chemometrics methods, such as exploratory data analysis, multiway data analysis, and data fusion. New chemometrics methods are continuously being updated and improved upon, two main distinctive characteristics are required: data exploration and graphical representation; and deep model validation through all steps of data processing. This also explains why chemometrics tools based on latent variables, for example, principal component analysis (PCA), soft independent modeling of class analogies (SIMCA), partial least squares (PLS), and PLS discriminant analysis (PLSDA), are still so popular and powerful. Nowadays, there is an established set of chemometric multiway methods and algorithms. The chapter mentions those that can serve the purposes of exploratory data analysis and classification, the tasks most frequently encountered in food authentication.
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.
2017
- Produzioni castanicole e identità territoriale: parliamone!
[Capitolo/Saggio]
Durante, Caterina; Ferrari, Erika; Foca, Giorgia; Benvenuti, Stefania; Tassi, Lorenzo
abstract
Il capitolo del volume tratta, in forma divulgativa, il problema della tracciabilità merceologica di alcune varietà castanicole della provincia di Modena. La caratterizzazione chimico-analitica effettuata su diversi campioni rappresentativi di altrettante cultivar geograficamente localizzate, consente la eventuale discriminazione delle varietà medesime. Il volume editato da Artestampa, appartiene ad una Collana che si sviluppa nel tempo, con l'obiettivo di far conoscere, descrivere e rappresentare alcune eccellenze agroalimentari e produzioni specifiche dei territori modenesi.
2016
- Analisi multivariata e spettroscopia NIR per la determinazione del grado di contaminazione da aflatossina M1 in latte bovino
[Abstract in Atti di Convegno]
LI VIGNI, Mario; Durante, Caterina; AMIGO RUBIO, JOSE' MANUEL; Cavallini, Nicola; Cocchi, Marina; Rizzi, N
abstract
La contaminazione alimentare da micotossine ha effetti importanti sull’opinione pubblica, come emerge in occasione di notizie relative a sequestri di prodotti contaminate. Queste molecole (potenziali cancerogeni) rappresentano una minaccia diretta alla salute e sicurezza per via della loro presenza ubiquitaria come contaminanti alimentari, siano essi prodotti vegetali ad uso diretto o semilavorati e, attraverso i mangimi, possono contaminare il latte e suoi derivati. La legislazione europea prevede un limite stringente per l’Aflatossina M1 nel latte (50 ppt): i metodi analitici quindi devono garantire elevata sensibilità, ottenuta al prezzo della velocità e semplicità di analisi (cromatografia), problematica parzialmente affrontata dai metodi immunologici (ELISA). In questo lavoro è valutata la fattibilità di un metodo analitico rapido ed efficente per la determinazione di AFM1 nel latte. L’obiettivo è ottenere un metodo rapido e semplice di screening da implementare ad ogni livello della filiera di produzione del latte, per realizzare un controllo interno capillare. Un totale di ottanta campioni di latte sono stati considerati, secondo quatnge di contaminazione: negativi (tossina assente), sotto il limite (20-50 ppt), sopra il limite (50-80 ppt), altamente contaminati (fino a 300 ppt). NIRS è già impiegata in questo contesto per la determinazione di proprietà del prodotto e controllo della qualità, pertanto è stata impiegata come metodo preliminare per la classificazione dei campioni secondo il livello di contaminazione. L’implementazione di un metodo rapido di screening in grado di definire se un campione cade in uno dei quattro gruppi sopracitati può rappresentare un importante vantaggio per ridurre il numero di campioni da sottoporre ad ulteriori accertamenti della contaminazione
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.
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
- 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 One- and Two-Dimensional NMR Spectroscopy for the Characterization of Protected Designation of Origin Lambrusco Wines of Modena
[Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; Graziosi, Riccardo; Silvestri, Michele; Bertacchini, Lucia; Durante, Caterina; Plessi, Maria
abstract
Lambrusco is a Protected Designation of Origin (P.D.O.) red wine of Modena (Italy) produced according to the production regulation (Decreto Ministeriale (D.M.) July 27th, 2009; G.U. n. 184-187-188, 13/08/2009). Here the use of 1H NMR spectroscopy as molecular fingerprints of several P.D.O. Lambrusco wines was proposed in order to serve as indicator of authenticity and quality control. Application of Partial Least Squares Discriminant Analysis (PLS-DA) revealed a good varietal discrimination by analyzing the low frequency spectral region. This model explains 68.8% of the variance for the Y vector (classification factor: varietal source). In particular, the signals of 2,3-butanediol, lactic, succinic and malic acids, and threonine were found to be the most statistically significant variables in the model. These findings seem to be very promising in the attempt to extend the study to geographical discrimination.
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
- Assessing feature relevance in NPLS models by VIP
[Articolo su rivista]
Favilla, Stefania; Durante, Caterina; LI VIGNI, Mario; Cocchi, Marina
abstract
Multilinear PLS (NPLS) and its discriminant version (NPLS-DA) are very diffuse tools to model multi-way data
arrays. Analysis of NPLS weights and NPLS regression coefficients allows data patterns, feature correlation
and covariance structure to be depicted. In this study we propose an extension of the Variable Importance
in Projection (VIP) parameter to multi-way arrays in order to highlight the most relevant features to predict
the studied dependent properties either for interpretative purposes or to operate feature selection. The VIPs
are implemented for each mode of the data array and in the case of multivariate dependent responses considering
both the cases of expressing VIP with respect to each single y-variable and of taking into account
all y-variables altogether.
Three different applications to real data are presented: i) NPLS has been used to model the properties of
bread loaves from near infrared spectra of dough, acquired at different leavening times, and corresponding
to different flour formulations. VIP values were used to assess the spectral regions mainly involved in determining
flour performance; ii) assessing the authenticity of extra virgin olive oils by NPLS-DA elaboration of
gas chromatography/mass spectrometry data (GC–MS). VIP values were used to assess both GC and MS discriminant
features; iii) NPLS analysis of a fMRI-BOLD experiment based on a pain paradigm of acute
prolonged pain in healthy volunteers, in order to reproduce efficiently the corresponding psychophysical
pain profiles. VIP values were used to identify the brain regions mainly involved in determining the pain intensity
profile.
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
- 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
- Exploratory Data Analysis
[Capitolo/Saggio]
LI VIGNI, Mario; Durante, Caterina; Cocchi, Marina
abstract
In the Food research and production field, system complexity is increasing and several new challenges are emerging every day. This implies a urgent necessity to extract information and obtain models capable of inferring the underlying relationships that link all the variability sources which characterize food or its production process (e.g. compositional profile, processing conditions) to very general end-properties of foodstuff, such as the healthiness, the consumer perception, the link to a territory and the effect of the production chain itself on food.
This makes a “deductive”, theory-driven research approach inefficient, since it is often difficult to formulate hypotheses. Explorative Multivariate Data Analysis methods, together with the most recent analytical instrumentation, offer the possibility to come back to an “inductive” data-driven attitude with a minimum of a priori hypotheses, instead helping in formulating new ones from the direct observation of data.
The aim of this Chapter is to offer the reader an overview of the most significant tools which can be used in a preliminary, exploratory phase, ranging from the most classical descriptive statistics methods, to Multivariate Analysis methods, with particular attention to Projection methods. For all techniques, examples are given so that the main advantage of this techniques, that is a direct, graphical representation of data and their characteristics, can be immediately experienced by the reader.
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
- 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
- 1D and 2D NMR application on balsamic and traditional balsamic vinegar of Modena
[Abstract in Rivista]
Bertelli, Davide; Papotti, Giulia; Graziosi, Riccardo; Durante, Caterina; Silvestri, Michele; Plessi, Maria
abstract
In recent years it has greatly increased the interest in analytical techniques able to certify the origin and authenticity of food along the production and distribution chains starting from raw materials to commercial products. The main difficulty in the foodstuff characterization is related to the complexity of the sample, which is often a complex mixture of several compounds present in concentration ratios very different from each other. The full characterization requires supplementary information from different techniques, therefore, non-separative analytical methods, that allow to obtain molecular fingerprints of complex mixtures can be particularly useful for the characterization and quality control and foodstuff authenticity and traceability. In this regard, in recent years has greatly increased the interest in the Nuclear Magnetic Resonance (NMR) and its use as a routine method for the analysis of complex mixtures as foods, balsamic vinegar among them, thanks to the availability of instruments at high magnetic fields and the consequent improvement of analytical sensitivity (Caligiani et al., 2007; Consonni et al., 2008). The aim of the present work was to select and optimize several 1D and 2D NMR sequences (1H-NMR, 1H-1H COSY, 1H-13C HMBC) to characterize the Balsamic vinegar of Modena and the Traditional Balsamic vinegar of Modena. The application of HR-NMR techniques to the samples has generated very complicated spectra that needed to be previously processed and subsequently analyzed by chemometric methods. To reduce the inhomogeneous proton NMR chemical shift of signals along the spectra, due to small pH changes and intermolecular interactions, all spectra were aligned using the toolbox Icoshift 1.0 for Matlab (Mathworks Inc., Natick, MA) (Savorani et al., 2010). Besides, to achieve a reliable classification of the different samples, unsupervised and supervised pattern recognition procedures were applied to the NMR data obtained.
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
- Computational Insights into ADAMTS4, ADAMTS5 andMMP13 Inhibitor Selectivity
[Articolo su rivista]
FILOMIA, Federico; SAXENA, PUNEET; DURANTE, Caterina; DE RIENZO, Francesca; COCCHI, Marina; MENZIANI, Maria Cristina
abstract
The results obtained by means of Molecular Dynamicssimulations and Multiway Explorative Data Analysison ADAMTS4, ADAMTS5 and MMP13 complexed with Marimastatand two cis-1(S)2(R)-amino-2-indanol ligands suggestthat determinant characteristics for ligand binding andselectivity among the three enzymes are to be found in thedifferent protein conformation flexibility. Moreover, the role of the TS-domain in the inhibitor binding to ADAMTS enzymeshas been investigated for the first time in this work.The results obtained suggest that the influence of the TSdomainon the S1’ loop fluctuations of ADAMTS4 andADAMTS5 could be exploited for the design of therapeuticsfor chronic osteoarthritis diseases.
2012
- Evaluation of the behaviour of fluorine-containing bioactive glasses: reactivity in a simulated body fluid solution assistedby multivariate data analysis
[Articolo su rivista]
Cocchi, Marina; Durante, Caterina; Lusvardi, Gigliola; Malavasi, Gianluca; Menabue, Ledi
abstract
Potentially bioactive fluorine-containing glassesof formula 46.2SiO224.3Na2O(26.9-x)CaO2.6P2O5xCaF2 [x = (0), 5, 10, 15] have been studied: the study wascarried out as a function of fluorine percentage, dimensionsand time of soaking in SBF. The results are compared tothose obtained in the same conditions for Bioglass 45S5.Due to the high number and different kind of variables/conditions explored by this set of data, the results arerationalized for the first time by means of multivariate dataanalysis (MDA); in this way it is possible to classify thebehaviour of bioglasses toward bioactivity. The presence offluorine does not inhibit the formation of HA; in particular,for a fast bioactivity (in term of HA crystallization) it willbe better to have large particle size or slabs, while for a fastdissolution fine particle sizes should be preferred.
2012
- HR-NMR studies for the characterization of DOC Lambrusco wines of Modena
[Abstract in Rivista]
Bertelli, Davide; Papotti, Giulia; Graziosi, Riccardo; Durante, Caterina; Bertacchini, Lucia; Plessi, Maria
abstract
NMR spectroscopy is currently recognized as an important tool in food science and analysis for the authentication and quality control of foodstuff. The wine area is definitely one of those in which the NMR has proved most successful in recent years. High-resolution techniques were rather powerful tools for studying minor components of oenological products. Classical studies on oenological products are normally based on composition data obtained by various analytical techniques, however, since the quality and characteristics of a product are not the simple sum of individual chemical characteristics, NMR analysis with chemometric data analysis certainly is a useful tool in this regard. Over the past few years, many works based on proton NMR coupled with multivariate data analysis were been conducted concerning the study of the usability of HR-NMR as fingerprint analysis tool in oenology. Between them in particular different authors have proved the validity to use this technique as an indirect indicator of geographical traceability and demonstrated that HR-NMR is an extremely powerful method for the study of oenological product and wine in particular (Brescia et al., 2002; Viggiani and Castiglione, 2008). In this context, the present work, which is part of the extensive research project AGER (Agroalimentare e Ricerca: New analytical methodologies for geographical and varietal traceability of oenological products), aimed to use the HR-NMR techniques as molecular fingerprints in order to serve as indirect indicators of authenticity and quality control of several DOC Lambrusco wines of Modena (Lambrusco di Sorbara, Lambrusco Salamino di Santa Croce and Lambrusco Grasparossa di Castelvetro) provided by local producers joined to the research project AGER. The data obtained were coupled with chemometric analysis tools to effectively interpret the complex results collected from mono and bi-dimensional spectra (HR-1H-NMR, 1H-1H COSY, 1H-13C HMBC) acquired.
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
- Modeling the Binding Affinity of p38a MAPKinase Inhibitors by Partial Least SquaresRegression
[Articolo su rivista]
Basant, Nikita; Durante, Caterina; Cocchi, Marina; Menziani, Maria Cristina
abstract
The p38 mitogen-activated protein kinase is activatedby environmental stress and cytokines andplays a role in transcriptional regulation andinflammatory responses. Factors influencing theactivity and selectivity of the p38a mitogen-activatedprotein kinase inhibitors have been investigatedin this paper by inspecting the bindingorientation and the possible residue-inhibitorinteractions in the binding site. The binding patternof a set of 45 different inhibitors against p38amitogen-activated protein kinase was studiedthrough Molecular Dynamic Simulations of theprotein-inhibitor complexes. Further, Partial LeastSquares regression was used to develop a QuantitativeStructure Activity Relationship model topredict the binding affinities of ligands. Theselected model successfully predicted the test setwith a Root Mean Square Error of Prediction of1.36. The regression coefficients and the VariableImportance in Projection plots highlighted the residue-inhibitor interactions which exhibited thelargest absolute effect on the ligand binding, suchas the van der Waals interaction with LYS50,ILE81, ASP165; electrostatic interactions withSER29, LEU164; hydrogen bonds with MET106;and total energy interaction with SER29 andLEU83.
2012
- NMR application on oenological products
[Relazione in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Graziosi, Riccardo; Silvestri, Michele; Durante, Caterina; Plessi, Maria
abstract
The present work, which is part of the extensive research project AGER - AGroalimentare E Ricerca (“New analytical methodologies for geographical and varietal traceability of oenological products”) coordinated by the University of Modena, aims to use the HR-NMR techniques as molecular fingerprints in order to serve as indirect indicators of authenticity and quality control. In this context, 110 PDO Protected Designation of Origin Lambrusco wines of Modena (34 Lambrusco di Sorbara, 38 Lambrusco Salamino di Santa Croce and 38 Lambrusco Grasparossa di Castelvetro) and several grape musts at different stage of winemaking, provided by local producers joined to the research project AGER - AGroalimentare E Ricerca, were analyzed. The data obtained were coupled with mono and multi variate chemometric analyses to effectively interpret the complex results collected from mono and bi-dimensional spectra (HR-1H-NMR, 1H-1H COSY, 1H-13C HMBC) acquired. Before statistical analysis, all mono-dimensional spectra were calibrated using the TMSP signal, whereas the bi-dimensional spectra were calibrated using one of the signals present in all the spectra analyzed. In this context, NMR spectroscopy represents an important tool for the authentication and quality control of foodstuff. The wine area, in particular, is one of those in which the NMR has proved most successful in recent years (Brescia et al., 2002; Viggiani and Castiglione, 2008). High-resolution techniques were rather powerful tools for studying minor components of oenological products. Since the quality and characteristics of a product are not the simple sum of individual chemical characteristics, NMR analysis with chemometric data analysis certainly is a useful tool in this regard. To the best of our knowledge, only a few studies were focused on geographical and varietal traceability of PDO Lambrusco wines of Modena, using simple 1D and 2D high-resolution NMR coupled with chemometrics directly on samples with minimal pretreatment.
2012
- Sistemi per la Tracciabilità, Autenticità e il Monitoraggio di Processo e Prodotto
[Spin Off]
Cocchi, Marina; Bertacchini, Lucia; Durante, Caterina; Favilla, Stefania; LI VIGNI, Mario; Silvestri, Michele
abstract
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
- A classification tool for N-way array based on SIMCA methodology
[Articolo su rivista]
Durante, Caterina; Rasmus, Bro; Cocchi, Marina
abstract
In the literature there are only fewpapers concerned with classification methods for multi-way arrays. The mostcommon procedure, by far, is to unfold the multi-way data array into an ordinary matrix and then to apply thetraditional multivariate tools for classification. As opposed to unfolding the data several possibilities exist forbuilding classification models more directly based on the multi-way structure of the data. As an example, multiwaypartial least squares discriminant analysis has been used as a supervised classification method, anotheralternative that has been investigated is to perform classification using Fisher's LDA or SIMCA on the score matrixfrom e.g. a PARAFAC or a Tucker model. Despite a few attempts of applying such multi-way classificationapproaches, no-one has looked into how such models are best built and implemented.In this work, the SIMCA method is extended to three-way arrays. Included in this work is also actual code thatwill work on general multi-way arrays rather than just three-way arrays. In analogy with two-way SIMCA, adecomposition model is separately built for the multi-way data for each class, using multi-way decompositionmethod such as PARAFAC or Tucker3. In the choice of the best class dimensionality, i.e. number of latent factors,both the results of cross-validation but mainly the sensitivity/specificity values are evaluated. In order toestimate the class limits for each class model, orthogonal and score distances are considered, and differentstatistics are implemented and tested to set confidence limits for these two parameters. Classificationperformance using different definitions of class boundaries and classification rules, including the use of crossvalidatedresiduals and scores is compared.The proposed N-SIMCA methodology and code, besides simulated data sets of varying dimensionality, has beentested on two case studies, concerning food authentication tasks for typical food products.
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
- Impiego di HR-NMR per la caratterizzazione dell'aceto balsamico tradizionale di Modena
[Relazione in Atti di Convegno]
Bertelli, Davide; Papotti, Giulia; M., Ciccotti; Durante, Caterina; Plessi, Maria
abstract
Negli ultimi anni è notevolmente aumentato l’interesse verso prove analitiche in grado di aiutare nella certificazione dell’origine e dell’autenticità degli alimenti lungo tutta la filiera di produzione e distribuzione a partire dalle materie prime fino ai prodotti posti in vendita. La difficoltà principale nella caratterizzazione dei prodotti alimentari è legata alla complessità del campione che quasi sempre si presenta come una miscela di molte componenti chimicamente differenti in rapporti estremamente diversi l’uno dall’altro; proprio per questo tutte le possibile tecniche analitiche sono d’interesse e spesso la piena caratterizzazione richiede informazioni complementari da parte di tecniche diverse. Per questa ragione diverse tecniche analitiche non separative, che permettono cioè di ottenere fingerprint molecolari di miscele complesse possono essere particolarmente utili per la caratterizzazione e la assicurazione di qualità, autenticità degli alimenti nonché per problemi legati alla tracciabilità, fra queste negli ultimi anni ha richiamato particolare attenzione Risonanza Magnetica Nucleare (NMR). Questa tecnica quando applicata a miscele complesse fornisce spettri la cui complessità è tale da essere difficilmente interpretabili solo con una semplice analisi classica dei segnali, per queste ragioni diventa imperativo l’uso di tecniche statistiche e chemiometriche per ottenere risultati e modelli realmente significativi. Scopo della presente ricerca, è stato quello di selezionare ed ottimizzare alcune sequenze NMR per lo studio e caratterizzazione dell’ Aceto Balsamico Tradizionale di Modena (ABTM). Le sequenze selezionate ed ottimizzate è stata poi testata su diversi campioni in relazione a semplici parametri analitici per verificare l’utilizzabilità di dati spettrali di questo tipo alla luce del futuro utilizzo come indicatore indiretto di tracciabilità geografica. Queste ricerche rappresentano la prima fase del più vasto progetto di ricerca MAAT, (Sviluppo di Metodi Analitici per l’Autenticazione e la Tracciabilità Geografica degli Alimenti), attualmente finanziato dalla Provincia di Modena e da diverse aziende private e consorzi di produttori di prodotti enologici tipici del territorio modenese. Le sequenze selezionate sono state in grado di ottenere dai campioni informazioni di fingerprint utili allo studio dell’ABTM e quindi potenzialmente sfruttabili come indicatori geografici.
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
- 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.
2010
- Molecular Dynamics Simulations of Sodium Silicate Glasses:Optimization and Limits of the Computational Procedure
[Articolo su rivista]
Pota, Marco; Pedone, Alfonso; Malavasi, Gianluca; Durante, Caterina; Cocchi, Marina; Menziani, Maria Cristina
abstract
The performance of the molecular dynamics (MD) simulations to obtain the structure of silica glasses containing different concentrations of alkali oxides has been tested. An optimal MD simulation procedure (including cooling cycle, MD constants and ensemble used) has been developed by means of experimental design methodologies (DOE), firstly restricting the study to the 30% Na2O silica glass for which experimental data are available to allow the comparison of the results. The optimization procedure led to simulations that well predict experimental density and short-range structure of glasses with different sodium content. On the contrary, the medium-range structure has been badly reproduced and it was not possible to determine a reliable correlation with the parameters of the simulation procedures used. Therefore, the correlation of medium-range properties with the structure has been studied by means of the PLS methods. The results showed to be useful to highlight the relationships among structural elements, such as radial distribution functions of specific bonds and angles, and Qn species, suggesting possible directions in order to improve the force field.
2010
- Wheat flour formulation by mixture design and multivariate study of its technological properties
[Articolo su rivista]
LI VIGNI, Mario; Durante, Caterina; Foca, Giorgia; Ulrici, Alessandro; Birthe Pontoppidan Møller, Jespersen; Rasmus, Bro; Cocchi, Marina
abstract
Wheat flour plays a pivotal role in determining the overall quality of bread (loaf dimensions, crumb texture and consistency). A precise knowledge of flour chemical and technological properties is of paramount importance for the baking industry, to tune the modifications of the recipe and production parameters. However, it is still common to have to deal with an empirical, trial and error-based approach, and generally, time consuming techniques are employed to determine the quality indexes for flour.In the context of an industrial bread-making process, this study addresses the evaluation of the effect of a systematic variation in the mixture composition of wheat flours on their properties. The main objective is to offer this field a more rigorous method to evaluate and improve flour properties, by employing experimental design methodologies and interpreting the results in a multivariate way, instead of the common one variable at a time approach. The results show that a careful planning of flour mixtures when testing new varieties and formulation helps to obtain meaningful and easy-to-understand results as far as their properties are concerned.
2009
- Discrimination of Healthy and Neoplastic Human Colon Tissues by ex Vivo HR-MAS NMR Spectroscopy and Chemometric Analyses
[Articolo su rivista]
V., Righi; Durante, Caterina; Cocchi, Marina; C., Calabrese; G., Di Febo; F., Lecce; A., Pisi; V., Tugnoli; Mucci, Adele; Schenetti, Luisa
abstract
The metabolic profile of human healthy and neoplastic colorectal tissues was obtained using ex vivo High-Resolution Magic Angle Spinning (HR-MAS) NMR spectroscopy. Principal Components Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA) were applied to NMR data in order to highlight the biochemical differences between healthy and neoplastic colorectal tissues. The synergic combination of ex vivo HR-MAS NMR spectroscopy with Multivariate Data Analysis enables discrimination between healthy and tumoral colorectal tissues and identification of the increase of taurine, acetate, lactate, and lipids, and the decrease of polyols and sugars as tumoral characteristics. Moreover, it was found that macroscopically/histologically normal colorectal tissues, collected at least 15 cm from the adenocarcinoma, are characterized by a metabolic pattern quite similar to that typical of tumoral lesions.It was shown that ex vivo HR-MAS NMR spectroscopy, performed on intact specimens, may be of great potentiality in the clinical evaluation of human neoplastic colorectal tissues and that thebiochemical data represent the molecular basis for an accurate and noninvasive clinical applications of in vivo NMR spectroscopy.
2009
- 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
- Wheat Flour formulation by Mixture Design and study of its properties and performance
[Relazione in Atti di Convegno]
LI VIGNI, Mario; Cocchi, Marina; Durante, Caterina; Ulrici, Alessandro; Foca, Giorgia; R., Bro; B. P., Møller Jespersen
abstract
-
2008
- At-line monitoring of the leavening process in industrial bread making by near infrared spectroscopy
[Articolo su rivista]
Ulrici, Alessandro; LI VIGNI, Mario; Durante, Caterina; Foca, Giorgia; P., Belloni; B., Brettagna; T., DE MARCO; Cocchi, Marina
abstract
The potential of near infrared (NIR) spectroscopy to characterise doughs for industrial bread making, directly at the production plant, was investigated. Different stages of dough processing have been monitored at-line, employing a Fourier transform-NIR instrument equipped with an optical fi bre. Parallel factors analysis has been used to study the spectral variation throughout the production line, with the aim of acquiring indications on the modifi cations the dough undergoes during the process. Moreover, wavelet interface for linear modelling analysis, which performs variable selection in the wavelet domain, has been employed to explore the possibility of monitoring the leavening step by identifying a relationship between the NIR signal and the leavening phase, considering the leavening time and the total titrable acidity of the dough. Results show that some aspects of the leavening process can be calibrated from the NIR spectra, thus corroborating the fact that the NIR signal is infl uenced by the modifi cations that occur along with the production process.
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
- Discrimination of healthy and neoplastic human colon tissues by ex vivo HR-MAS NMR spectroscopy and chemometric analyses
[Abstract in Atti di Convegno]
V., Righi; Durante, Caterina; Cocchi, Marina; C., Calabrese; V., Tugnoli; Mucci, Adele; Schenetti, Luisa
abstract
The metabolic profile of human healthy and neoplastic colorectal tissues was obtained using ex vivo High-Resolution Magic Angle Spinning (HR-MAS) NMR spectroscopy. Principal Components Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-DA) were applied to NMR data in order to highlight the biochemical differences between healthy and neoplastic colorectal tissues.
2008
- Metabolic profiles of healthy and neoplastic human colorectal tissues studied by ex vivo HR-MAS MRS
[Relazione in Atti di Convegno]
V., Righi; Mucci, Adele; Schenetti, Luisa; C., Calabrese; Cocchi, Marina; Durante, Caterina; V., Tugnoli
abstract
The metabolic profile of human healthy and neoplastic colorectal tissues was obtained through ex vivo HR-MAS MRS and studied through chemometric analyses.
2008
- Mitochondrial DNA Haplogroups and Highly Active Antiretroviral Therapy–Related Lipodystrophy
[Articolo su rivista]
Nasi, Milena; Guaraldi, Giovanni; Gabriella, Orlando; Caterina, Durante; Pinti, Marcello; Elisa, Nemes; Nardini, Giulia; Giuseppe, Passarino; Cocchi, Marina; Esposito, Roberto; Mussini, Cristina; Cossarizza, Andrea
abstract
Background. The combination of different point mutations in mitochondrial DNA (mtDNA), which are defined as haplogroups, may cause modification in organelle function and may be involved in several pathologies. We analyzed the distribution of mtDNA polymorphisms in human immunodeficiency virus (HIV)–infected patients with lipodystrophy, a relevant adverse event caused by highly active antiretroviral therapy, and their correlation with metabolic and viroimmunologic parameters. Methods. The frequency of the 9 most common European haplogroups was investigated in 346 white, HIV- infected patients with lipodystrophy. Haplogroups were identified on the basis of classic methods. Statistical analysis was performed with use of 1-way analysis of variance, the x2 test, and principal-components analysis. Results. The distribution of mtDNA haplogroups among patients with lipodystrophy was similar to that among the general European population. We found no differences between patients with different haplogroups with regard to viroimmunologic results (plasma HIV load, CD4+ T cell count, and nadir CD4+ T cell count), glucose data (glucose, insulin, C-peptide, and glycosylated hemoglobin concentrations and insulin resistance), lipid data (levels of triglycerides, total cholesterol, high- and low-density lipoproteins, and apolipoprotein A1 and B), acid-base balance parameters (lactate level and anion gap), or anthropometric measures (weight, body mass index, and waist- to-hip ratio). No differences were observed in trunk fat levels, leg-fat ratio (which was determined by dual-energy X-ray absorptiometry), or exposure to different drug classes. Principal-components analysis confirmed that the spatial distribution of patients belonging to a given haplogroup was not influenced by different clinical parameters. Conclusions. Our study indicates that, in HIV-infected patients with lipodystrophy, mtDNA haplogroups are not related to major metabolic changes or to particular viroimmunologic features.
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
- Neoplasms of the gastro-intestinal tract characterized by HR-MAS NMR
[Abstract in Atti di Convegno]
Mucci, Adele; V., Righi; C., Calabrese; Cocchi, Marina; Durante, Caterina; V., Tugnoli; Schenetti, Luisa
abstract
The results of our studies (HR-MAS NMR and statistical analysis) on healthy stomach and colon mucosa, and on gastric and colon adenocarcinomas are presented.
2008
- 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
- 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
- Efficient variables selection in multivariate analysis of signals by coupling fast wavelet transform and genetic algorithms
[Relazione in Atti di Convegno]
Cocchi, Marina; Durante, Caterina; Foca, Giorgia; LI VIGNI, Mario; Leardi, R; Ulrici, Alessandro
abstract
-
2007
- Elaboration and Application of Algorithms Performing Feature Selection in the Wavelet Domain for Analysis of NIR based data
[Relazione in Atti di Convegno]
Cocchi, Marina; Durante, Caterina; LI VIGNI, Mario; Foca, Giorgia; Ulrici, Alessandro
abstract
-
2007
- HR-MAS NMR e analisi multivariata di neoplasie umane colo-rettali
[Abstract in Atti di Convegno]
V., Righi; Durante, Caterina; Cocchi, Marina; V., Tugnoli; Mucci, Adele; Schenetti, Luisa
abstract
E' riportato uno studio basato sull'applicazione dell'HR-MAS NMR e dell'analisi multivariata a neoplasie umane colo-rettali.
2007
- 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
-
2007
- Subject classification obtained by cluster analysis and principal component analysis applied to flow cytometric data
[Articolo su rivista]
Lugli, Enrico; Pinti, Marcello; Nasi, Milena; Troiano, Leonarda; Ferraresi, Roberta; Mussi, Chiara; Salvioli, Gianfranco; Patsekin, V; Robinson, Jp; Durante, Caterina; Cocchi, Marina; Cossarizza, Andrea
abstract
BACKGROUND: Polychromatic flow cytometry (PFC) allows the simultaneous determination of multiple antigens in the same cell, resulting in the generation of a high number of subsets. As a consequence, data analysis is the main difficulty with this technology. Here we show the use of cluster analysis (CA) and principal component analyses (PCA) to simplify multicolor data visualization and to allow subjects' classification. METHODS: By eight-colour cytofluorimetric analysis, we investigated the T cell compartment in donors of different age (young, middle-aged, and centenarians). T cell subsets were identified by combining positive and negative expression of antigens. The resulting data set was organized into a matrix and subjected to CA and PCA. RESULTS: CA clustered people of different ages on the basis of cytofluorimetric profile. PCA of the cellular subsets identified centenarians within a different cluster from young donors, while middle-aged donors were scattered between these groups. These approaches identified T cell phenotypes that changed with increasing age. In young donors, memory T cell subsets tended to be CD127+ and CD95- whereas CD127-, CD95+ phenotypes were found at higher frequencies in people with advanced age. CONCLUSIONS: Our data suggest the use of bioinformatic approaches to analyze large data-sets generated by PFC and to obtain the rapid identification of key populations that best characterize a group of subjects. (c) 2007 International Society for Analytical Cytology.
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
- Applicazione di algoritmi per la selezione di variabili nell’analisi di spettri NIR di prodotti alimentari
[Relazione in Atti di Convegno]
Cocchi, Marina; Ulrici, Alessandro; Foca, Giorgia; Durante, Caterina
abstract
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2006
- Classificazione chemiometrica di spettri NIR di frammenti ossei di specie animali diverse
[Relazione in Atti di Convegno]
Cocchi, Marina; Pavino, D; Ulrici, Alessandro; Foca, Giorgia; Durante, Caterina; Martra, G; Abete, M. C.
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
- Modulation of CD38 expression in human longevity: A flow cytometric study
[Abstract in Atti di Convegno]
Lugli, Enrico; Pinti, Marcello; Troiano, Leonarda; Nasi, Milena; Ferraresi, Roberta; Roat, Erika; Durante, Caterina; Cocchi, Marina; Cossarizza, Andrea
abstract
The dynamics of CD38 expression innewborns and young healthy donors hasbeen widely investigated for many years.However, little is known about the modulationof this marker during humanageing. We analyzed the changes inCD38 expression in peripheral bloodlymphocytes (PBL) from subjects whowere centenarians. For this purpose weused polychromatic flow cytometry, apowerful technology that allows the determinationof multiple antigens (in ourcase, up to 8) present in the same cell.Among the subsets within CD4+ andCD8+ T cell populations identified bythis approach, we investigated the expressionof CD38 together with markersrelated to extrathymic T cell differentiation(CD45RA and CCR7), T cell survival(CD127/IL-7rα) and activation/apoptosis(CD95). The groups analysed includedyoung donors (21±2 years old),middle-aged individuals (60±1.5 yearsold) and centenarians.By automatic boolean gating, we identifiedall the possible subsets obtained bythe combination of positive and negativeexpression for each marker indicatedabove. Moreover, we could distinguish betweendim or bright expression of CD38.CD38 expressed by CD4+ T cells doesnot show significant modifications in thethree samples either in of the virgin ormemory subsets.A slight increase in CD38 expressionwas found in PBL CD8+ T cells from centenarians.These CD8+/38dim T cells displayeda CD45RA-/CCR7+ central memoryor CD45RA-/CCR7- effector memoryphenotype. Further, CD38 expressionwas associated with the presence ofCD95 and the absence of CD127/IL-7rα.These results were also confirmed byCluster Analysis (CA) and PrincipalComponent Analysis (PCA) of the highnumber of T cell populations identifiedby flow cytometry. These bioinformatictechniques cluster the individuals accordingto the flow cytometric profile,which confirmed that the subsets with anincreased expression of CD38 (CD38bright) are more frequent in the sampleof centenarians.In conclusion, our data indicate amodulation of CD38 expression in CD8+T cells during human ageing. In particular,the preferential coexpression of thisantigen with CD95 but not CD127/IL-7r_suggests an age-dependent acquisition ofan effector phenotype of CD8+ T cellswhich could, at least in part, explain thechronic pro-inflammatory status presentin centenarians.
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.
2005
- Application of fast fourier transform cross-correlation for the alignment of large chromatographic and spectral datasets
[Articolo su rivista]
Wong, J. W. H.; Durante, C.; Cartwright, H. M.
abstract
Preprocessing of Chromatographic and spectral data is an important aspect of analytical sciences. In particular, recent advances in proteomics have resulted in the generation of large data sets that require analysis. To assist accurate comparison of chemical signals, we propose two methods for the alignment of multiple spectral data sets. Based on methods previously described, each Chromatograph or spectrum to be aligned is divided and aligned as individual segments to a reference. However, our methods make use of fast Fourier transform for the rapid computation of a cross-correlation function that enables alignments between samples to be optimized. The proposed methods are demonstrated in comparison with an existing method on a chromatographic and a mass spectral data set. It is shown that our methods provide an advantage of speed and a reduction of the number of input parameters required. The software implementations for the proposed alignment methods are available under the downloads section at http://ptcl.chem.ox.ac.uk/~jwong/specalign. © 2005 American Chemical Society.
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.
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.
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.