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Davide BERTELLI

Professore Associato
Dipartimento Scienze della Vita sede ex Scienze Farmaceutiche Via Campi 103


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Pubblicazioni

2024 - Alginate-Based Carriers Loaded with Mulberry (Morus alba L.) Leaf Extract: A Promising Strategy for Prolonging 1-Deoxynojirimicyn (DNJ) Systemic Activity for the Nutraceutical Management of Hyperglycemic Conditions [Articolo su rivista]
Marchetti, Lucia; Truzzi, Eleonora; Rossi, Maria Cecilia; Benvenuti, Stefania; Cappellozza, Silvia; Saviane, Alessio; Bogataj, Luca; Siligardi, Cristina; Bertelli, Davide
abstract


2024 - Phytochemical and functional characterization of cultivated varieties of Morus alba L. fruits grown in Italy [Articolo su rivista]
Truzzi, E.; Marchetti, L.; Gibertini, G.; Benvenuti, S.; Cappellozza, S.; Giovannini, D.; Saviane, A.; Sirri, S.; Pinetti, D.; Assirelli, A.; Bertelli, D.
abstract

: Morus alba L. fruits are considered functional foods with an important nutritional value for their high content of polyphenols. Therefore, the type and level of phytochemicals of the soroses from 13 M. alba cultivars grown in Italy were characterized due to the lack of data available about their nutraceutical properties. Mature M. alba fruits exhibited variable polyphenol, flavonoid, anthocyanin, proanthocyanins, and 1-deoxynojirimycin contents which resulted in different antioxidant and α-glucosidase inhibitory activities. Regression models built on UHPLC-HRMS results revealed a strong correlation between the expression of quercetin derivatives, cyanidin 3-O-glucoside, caffeoyl methyl quinates, and 5,5'-dehydrodivanillic acid, and the biological activity of each fruit. On another note, principal component analysis revealed that the quantity of caffeoyl/dicaffeoyl methyl quinate, caffeoylquinic acids, and quercetin derivatives decreased during ripening. The results on the compositional and functional characterization of mature M. alba fruits might improve their consumption and economic value in Italy.


2024 - 1H NMR targeted and untargeted approaches for the authentication of milk chocolates [Articolo su rivista]
Truzzi, Eleonora; Rossi, Maria Cecilia; Bertelli, Davide
abstract


2023 - Capitolo 15: Vino [Capitolo/Saggio]
Bertelli, Davide; Caligiani, Augusta; Mannina, Luisa; Marchetti, Lucia; Spano, Mattia
abstract


2023 - Capitolo 16: prodotti dell'alveare [Capitolo/Saggio]
Bertelli, Davide; Marchetti, Lucia; Menegazzo, Ileana; Schievano, Elisabetta
abstract


2023 - Combination of Nanodelivery Systems and Constituents Derived from Novel Foods: A Comprehensive Review [Articolo su rivista]
Truzzi, E.; Bertelli, D.; Bilia, A. R.; Vanti, G.; Maretti, E.; Leo, E.
abstract

: Novel Food is a new category of food, regulated by the European Union Directive No. 2015/2283. This latter norm defines a food as "Novel" if it was not used "for human consumption to a significant degree within the Union before the date of entry into force of that regulation, namely 15 May 1997". Recently, Novel Foods have received increased interest from researchers worldwide. In this sense, the key areas of interest are the discovery of new benefits for human health and the exploitation of these novel sources of materials in new fields of application. An emerging area in the pharmaceutical and medicinal fields is nanotechnology, which deals with the development of new delivery systems at a nanometric scale. In this context, this review aims to summarize the recent advances on the design and characterization of nanodelivery systems based on materials belonging to the Novel Food list, as well as on nanoceutical products formulated for delivering compounds derived from Novel Foods. Additionally, the safety hazard of using nanoparticles in food products, i.e., food supplements, has been discussed in view of the current European regulation, which considers nanomaterials as Novel Foods.


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


2023 - Multivariate Statistical Models for the Authentication of Traditional Balsamic Vinegar of Modena and Balsamic Vinegar of Modena on 1H-NMR Data: Comparison of Targeted and Untargeted Approaches [Articolo su rivista]
Truzzi, Eleonora; Marchetti, Lucia; Piazza, Danny Vincenzo; Bertelli, Davide
abstract

This work aimed to compare targeted and untargeted approaches based on NMR data for the construction of classification models for Traditional Balsamic Vinegar of Modena (TBVM) and Balsamic Vinegar of Modena (BVM). Their complexity in terms of composition makes the authentication of these products difficult, which requires the employment of several time-consuming analytical methods. Here, 1H-NMR spectroscopy was selected as the analytical method for the analysis of TVBM and BVM due to its rapidity and efficacy in food authentication. 1H-NMR spectra of old (>12 years) and extra-old (>25 years) TVBM and BVM (>60 days) and aged (>3 years) BVM were acquired, and targeted and untargeted approaches were used for building unsupervised and supervised multivariate statistical modes. Targeted and untargeted approaches were based on quantitative results of peculiar compounds present in vinegar obtained through qNMR, and all spectral variables, respectively. Several classification models were employed, and linear discriminant analysis (LDA) demonstrated sensitivity and specificity percentages higher than 85% for both approaches. The most important discriminating variables were glucose, fructose, and 5-hydroxymethylfurfural. The untargeted approach proved to be the most promising strategy for the construction of LDA models of authentication for TVBM and BVM due to its easier applicability, rapidity, and slightly higher predictive performance. The proposed method for authenticating TBVM and BVM could be employed by Italian producers for safeguarding their valuable products.


2023 - NMR-based analytical methods for quantifying boswellic acids in extracts employed for producing food supplements: comparison of 13C-qNMR and 1H-NMR/PLS-R methods [Articolo su rivista]
Truzzi, E.; Piazza, D. V.; Rossi, M. C.; Benvenuti, S.; Bertelli, D.
abstract

The content of boswellic acids (BAs) in Boswellia serrata extracts employed for producing food supplements is often overestimated due to the use of conventional non-selective quantification methods. Here, the applicability of NMR spectroscopy for the quality control of B. serrata extracts was evaluated by employing different strategies: C-13-quantitative NMR (qNMR) and H-1-NMR coupled with chemometrics. The C-13-qNMR demonstrated high precision and accuracy, but long-lasting acquisition times. C-13-qNMR quantitative results were used to build a PLS-R model on the H-1-NMR spectra to generate a faster analytical method. The R-2 and the RMSE in prediction were 0.925 and 5.878 respectively, indicating good model performances, which can be improved by increasing the number of extracts. Moreover, the identification of 3 extracts out of 33 without any trace of BAs underlined the importance of proper controls of the starting material to produce BA-based food supplements.


2023 - Novel application of 1H NMR spectroscopy coupled with chemometrics for the authentication of dark chocolate [Articolo su rivista]
Truzzi, Eleonora; Marchetti, Lucia; Fratagnoli, Arianna; Rossi, Maria Cecilia; Bertelli, Davide
abstract

The applicability of 1H NMR spectroscopy coupled with chemometric in the quality control of dark chocolate was investigated for the first time to detect cocoa-butter equivalents (CBEs) above the allowed limit by European regulation. Blends of chocolate-fats with CBEs in the range 0-50 % were prepared and analyzed by 1H NMR spectroscopy. Datasets composed of peaks' areas or spectral variables (fingerprinting) in glycerol region were tested for the creation of multivariate statistical models. Partial least-squares discriminant analysis (PLS-DA) and regression (PLS-R) methods were used to correctly identify the type of CBE and quantify its concentration respectively. The performances of the models created on the two datasets were evaluated in terms of chemo-metric indicators and compared. The robustness of models was investigated through the analysis of test sets and random permutation tests. Fingerprinting models revealed fruitful results in classifying and quantifying CBEs in blends demonstrating the applicability of NMR in chocolate quality control.


2023 - Potential of Full-Fat Silkworm-Based Diets for Laying Quails: Performance and Egg Physical Quality [Articolo su rivista]
Singh, Yazavinder; Cullere, Marco; Bertelli, Davide; Segato, Severino; Franzo, Giovanni; Frangipane di Regalbono, Antonio; Catellani, Paolo; Taccioli, Cristian; Cappellozza, Silvia; Dalle Zotte, Antonella
abstract


2023 - Sistema per il rilascio controllato di 1-desossinojirimicina [Brevetto]
Truzzi, Eleonora; Marchetti, Lucia; Bertelli, Davide; Cappellozza, Silvia; Saviane, Alessio
abstract


2022 - Characterization and Valorization of the Agricultural Waste Obtained from Lavandula Steam Distillation for Its Reuse in the Food and Pharmaceutical Fields [Articolo su rivista]
Truzzi, Eleonora; Chaouch, Mohamed Aymen; Rossi, Gaia; Tagliazucchi, Lorenzo; Bertelli, Davide; Benvenuti, Stefania
abstract


2022 - Disclosing the Antioxidant and Neuroprotective Activity of an Anthocyanin-Rich Extract from Sweet Cherry (Prunus avium L.) Using In Vitro and In Vivo Models [Articolo su rivista]
Filaferro, M.; Codeluppi, A.; Brighenti, V.; Cimurri, F.; Gonzalez-Paramas, A. M.; Santos-Buelga, C.; Bertelli, D.; Pellati, F.; Vitale, G.
abstract

In this study, an autochthonous variety of sweet cherry (Prunus avium L.), namely “Moretta di Vignola”, was processed to prepare extracts rich in polyphenols, which were characterized by high-performance liquid chromatography (HPLC) separation coupled to UV/DAD and ESI-MSn analysis. Then, a sweet cherry anthocyanin-rich extract (ACE) was prepared, fully characterized and tested for its activity against Parkinson’s disease (PD) in cellular (BV2 microglia and SH-SY5Y neuroblastoma) and in Drosophila melanogaster rotenone (ROT)-induced model. The extract was also evaluated for its antioxidant activity on Caenorhabditis elegans by assessing nematode resistance to thermal stress. In both cell lines, ACE reduced ROT-induced cell death and it decreased, alone, cellular reactive oxygen species (ROS) content while reinstating control-like ROS values after ROT-induced ROS rise, albeit at different concentrations of both compounds. Moreover, ACE mitigated SH-SY5Y cell cytotoxicity in a non-contact co-culture assay with cell-free supernatants from ROT-treated BV-2 cells. ACE, at 50 µg/mL, ameliorated ROT (250 µM)-provoked spontaneous (24 h duration) and induced (after 3 and 7 days) locomotor activity impairment in D. melanogaster and it also increased survival and counteracted the decrease in fly lifespan registered after exposure to the ROT. Moreover, heads from flies treated with ACE showed a non-significant decrease in ROS levels, while those exposed to ROT markedly increased ROS levels if compared to controls. ACE + ROT significantly placed the ROS content to intermediate values between those of controls and ROT alone. Finally, ACE at 25 µg/mL produced a significant increase in the survival rate of nematodes submitted to thermal stress (35 °C, 6–8 h), at the 2nd and 9th day of adulthood. All in all, ACE from Moretta cherries can be an attractive candidate to formulate a nutraceutical product to be used for the prevention of oxidative stress-induced disorders and related neurodegenerative diseases.


2022 - In vitro bioactivity evaluation of mulberry leaf extracts as nutraceutical for the management of diabete mellitus [Articolo su rivista]
Marchetti, Lucia; Truzzi, Eleonora; Frosi, Ilaria; Papetti, Adele; Cappellozza, Silvia; Saviane, Alessio; Pellati, Federica; Bertelli, Davide
abstract


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.


2021 - A novel qnmr application for the quantification of vegetable oils used as adulterants in essential oils [Articolo su rivista]
Truzzi, E.; Marchetti, L.; Benvenuti, S.; Righi, V.; Rossi, M. C.; Gallo, V.; Bertelli, D.
abstract

Essential oils (EOs) are more and more frequently adulterated due to their wide usage and large profit, for this reason accurate and precise authentication techniques are essential. This work aims at the application of qNMR as a versatile tool for the quantification of vegetable oils potentially usable as adulterants or diluents in EOs. This approach is based on the quantification of both1H and13C glycerol backbone signals, which are actually present in each vegetable oil containing triglycerides. For the validation, binary mixtures of rosemary EO and corn oil (0.8–50%) were prepared. To verify the general feasibility of this technique, other different mixtures including lavender, citronella, orange and peanut, almond, sunflower, and soy seed oils were analyzed. The results showed that the efficacy of this approach does not depend on the specific combination of EO and vegetable oil, ensuring its versatility. The method was able to determine the adulterant, with a mean accuracy of 91.81 and 89.77% for calculations made on1H and13C spectra, respectively. The high precision and accuracy here observed, make1H-qNMR competitive with other well-established techniques. Considering the current importance of quality control of EOs to avoid fraudulent practices, this work can be considered pioneering and promising.


2021 - Attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy coupled with chemometric analysis for detection and quantification of adulteration in lavender and citronella essential oils [Articolo su rivista]
Truzzi, E.; Marchetti, L.; Bertelli, D.; Benvenuti, S.
abstract

Introduction: The growing consumer interest in “naturals” led to an increased application of essential oils (EOs). The market outbreak induced the intensification of EO adulterations, which could affect their quality. Objectives: Nowadays, little is known about the illegal practice of adulteration of EOs with vegetable oils. Therefore, the application of mid-infrared spectroscopy coupled with chemometrics was proposed for the detection of EO counterfeits. Materials and methods: Two EOs, three seed oils, and their mixtures were selected to build the adulteration model. EO–adulterant mixtures for model calibration and validation were analyzed by attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy. The spectral data were analyzed with principal component analysis (PCA) and partial least-squares (PLS) regression. Results: PCA allowed the discrimination of the EO and adulterant percentages by explaining 97.47% of the total spectral variance with two principal components. A PLS regression model was generated with three factors explaining 97.73% and 99.69% of the total variance in X and Y, respectively. The root mean square error of calibration and the root mean square error of cross-validation were 0.918 and 1.049, respectively. The root mean square error of prediction value obtained from the external validation set was 1.588 and the coefficients of determination R2CAL and R2CV were 0.997 and 0.996, respectively. Conclusions: The results highlighted the robustness of the developed method in quantifying counterfeits in the range from 0 to 50% of adulterants, disregarding the type of EO and adulterant employed. The present work offers a research advance and makes an important impact in phytochemistry, revealing an easily applicable method for EO quality assessment.


2021 - Determination of 1-deoxynojirimycin (1-dnj) in leaves of italian or italy-adapted cultivars of mulberry (morus sp.pl.) by hplc-ms [Articolo su rivista]
Marchetti, L.; Saviane, A.; Monta, A. D.; Paglia, G.; Pellati, F.; Benvenuti, S.; Bertelli, D.; Cappellozza, S.
abstract

Recently, 1-DNJ has been widely studied by scientists for its capacity to inhibit α-gluco-sidase and reduce postprandial blood glucose and fat accumulation. To the best of our knowledge, this is the first analytical determination of 1-DNJ in Morus sp.pl. leaves carried out on Italian crops, and it could be used as a reference to assess the quality of the plant material in comparison to Far Eastern Asia cultivations. The effects of two thermal treatments were compared to test the incidence of the drying process on the 1-DNJ extractability. In addition, two harvesting seasons in the same year (2017) and two subsequent harvesting years (2017–2018) were considered. The amount of 1-DNJ herein found was comparable to that reported in the scientific literature for Asian cultivations. The increase in 1-DNJ along the summer and the higher level of this compound in the apical leaves also complies with previous findings. However, a strong implication for the climatic conditions in the different years and a significant interaction between climate and genotypes suggest exploring very carefully the agronomic practices and selecting cultivars according to different environmental conditions with a view to standardize the 1-DNJ amount in leaves.


2021 - Effect of a dietary inclusion of full-fat or defatted silkworm pupa meal on the nutrient digestibility and faecal microbiome of fattening quails [Articolo su rivista]
Dalle Zotte, A.; Singh, Y.; Squartini, A.; Stefanato, P.; Cappellozza, S.; Kovitvadhi, A.; Subaneg, S.; Bertelli, Davide; Cullere, M.
abstract

Silkworm (Bombyx mori L.) pupae are a by-product derived from silk production, which is often treated as waste and thus discarded: this can cause serious environmental problems and a loss of nutrients. Silkworm pupae are a rich source of protein and lipids, and the resulting protein meal can provide promising outcomes as livestock feed, notably for monogastric species. However, one possible issue that needs to be considered is the possible implication of the 1-Deoxynojirimycin (1-DNJ), a bio-compound of the silkworm that impairs glucose absorption, in poultry nutrition. Therefore, the present study evaluated the effect of the dietary inclusion of full-fat or defatted silkworm pupa meal (SWM) on the apparent digestibility of nutrients, feed choice and faecal microbiome in meat-producing quails. For the digestibility trial, a total of thirty-three 27-day-old Japanese quails (Coturnix coturnix japonica) were individually housed in digestibility cages and received three experimental diets: a control diet (control, commercial feed for fattening quails), and two other diets containing the 12.5% of either a full-fat SWM (SWM-FULL) or a defatted SWM (SWM-DEF). Subsequently, twenty-seven 33-day-old quails were simultaneously provided with Control, SWM-FULL and SWM-DEF diets for a 10-day feed choice trial. The results of the digestibility trial showed that the DM intake and excreta production were higher in both SWM groups than in the Control one (P < 0.001). The apparent digestibility of DM, organic matter, CP, ether extract , starch and energy was lower in both SWM groups than in the ccontrol group (P < 0.001), suggesting the possible implication of chitin and 1-DNJ. The feed choice test showed that quails preferred the Control diet (P < 0.001). From the microbiome analysis of the excreta, families such as Streptococcaceae (P < 0.05), Rikenellaceae and Eubacteriaceae (P < 0.01) and taxa at species level such as Lactobacillus delbrueckii (P < 0.05), Aneurinibacillus thermoaerophilus and Bacillus thermoamylovorans (P < 0.01) scored higher in SWM-FULL quails than in SWM-DEF and Control treatments. The present study demonstrated that a successful dietary inclusion of SWM for fattening quails needs to overcome the digestive criticalities caused by the of presence specific bio-compounds, namely chitin and 1-DNJ.


2021 - Effects of biostimulants on the chemical composition of essential oil and hydrosol of lavandin (Lavandula x intermedia emeric ex loisel.) cultivated in tuscan-emilian apennines [Articolo su rivista]
Truzzi, E.; Benvenuti, S.; Bertelli, D.; Francia, E.; Ronga, D.
abstract

In recent years, it has been shown that biostimulants can efficiently enhance plant metabolic processes, leading to an increased production of essential oil (EO) in aromatic plants. The present study aimed to evaluate the effects of two different commercial biostimulants composed of amino acids and seaweed extract, normally used for food organic crops, on the production and composition of EO and hydrosol of Lavandula x intermedia, cultivar “Grosso”. The products were applied during 2020 growing season on lavender crops in three different locations of the Northern Italian (Emilia-Romagna Region) Apennines. Plants were harvested and EOs extracted by steam distillation and analyzed by gas chromatography. Both biostimulants affected the yield of EO per plant (+11% to +49% depending on the treatment/farm combination) without significantly changing the chemical composition of EOs and hydrosols. Conversely, the composition of EOs and hydrosols are related to the location, and the main compounds of “Grosso” cultivar, limonene, 1,8-cineole, cis-ocimene, linalool, camphor, borneol, terpinen-4-ol, and linalyl acetate, show different ratios at the experimental test sites. The differences might be due to the sunlight exposure and various maintenance of the crops over the years. In conclusion, these results suggest that the employment of biostimulants on lavandin crops do not endanger the quality of the EO while increasing biomass production and promoting the sustainability of the crop.


2021 - HR‐1H NMR spectroscopy and multivariate statistical analysis to determine the composition of herbal mixtures for infusions [Articolo su rivista]
Marchetti, Lucia; Rossi, Maria Cecilia; Pellati, Federica; Benvenuti, Stefania; Bertelli, Davide
abstract

This study aims to verify the potential of proton nuclear magnetic resonance (1H‐NMR) combined with partial least square regression to determine the composition of herbal mixtures. NMR one‐dimensional nuclear Overhauser effect spectroscopy (1D‐NOESY) spectra were analyzed to extract significant information from the raw data. The best performing model included four factors explaining 88.70 and 83.77% of the total variance in X and Y, respectively. These promising results have laid the basis for further development of the method, useful also for the analysis of commercial herbal infusions.


2021 - Novel Strategy for the Recognition of Adulterant Vegetable Oils in Essential Oils Commonly Used in Food Industries by Applying 13C NMR Spectroscopy [Articolo su rivista]
Truzzi, Eleonora; Marchetti, Lucia; Benvenuti, Stefania; Ferroni, Annalisa; Rossi, Maria Cecilia; Bertelli, Davide
abstract

Essential oils (EOs) are valuable products commonly employed in the food industry and intensively studied as biopreservatives for the extension of food shelf-life. Unfortunately, EOs might be counterfeit to increase industrial profits. Among the possible adulterants, vegetable oils (VOs) must be considered for their characteristics and low costs. We aimed to apply nuclear magnetic resonance (NMR) spectroscopy for the detection and identification of VOs in mixtures with EOs. This innovative strategy is based on comparing the peak area ratio matrices of characteristic VO 13C NMR fatty acid signals with those of adulterated EOs. The identification of the VOs was achieved by calculating the matrix similarity at different confidence levels. The strategy demonstrated the capacity to efficiently recognize the presence of adulteration and the type of VO adulterant in mixtures. Thus, the method was applied to 20 commercial EOs, and VOs were detected and then identified in four samples.


2021 - Optimization and Validation of a High-Performance Liquid Chromatography Method for the Analysis of Hesperidin and Carvacrol for Veterinary Use [Articolo su rivista]
Truzzi, E.; Benvenuti, S.; Bertelli, D.; Scozzoli, M.
abstract

Plant-derived compounds have been recognized by the feed industry as important supplements for livestock welfare and health. In this context, Citrus aurantium L. extract and Origanum vulgare L. essential oil have been demonstrated to have strong anti-inflammatory and antioxidant effects on animals. Being the composition of plant-derived extracts extremely influenced by the environmental and growing conditions of the plants, quality control is necessary in terms of the concentration of the active compounds to assure the reproducibility of natural feed additives. The present work aimed at the validation of the extraction procedure from feed additives of Hesperidin (HES) and Carvacrol (CAR), the main active compounds of Citrus aurantium and Origanum vulgare extracts. Then, the quantification method of both the analytes was developed and validated by reversed high-performance liquid chromatography coupled with a UV detector. The validated method was tested on premixtures and final feed additives supplied by a local feed factory to supervise the production chain. The extraction method with methanol resulted to be efficient and highly reproducible, with recovery higher than 90% for both the analytes. The chromatographic method has been demonstrated to be accurate, precise (relative standard deviation percent lower than 2.06%), and linear in the tested range concentrations, with regression coefficients equal to 0.995 and 0.999 for HES and CAR respectively. The method demonstrated that the feed additives prepared by the factory by diluting the premixtures were less concentrated than what was declared on the label.


2021 - Separation and non-separation methods for the analysis of cannabinoids in Cannabis sativa L [Articolo su rivista]
Brighenti, V.; Marchetti, L.; Anceschi, L.; Protti, M.; Verri, P.; Pollastro, F.; Mercolini, L.; Bertelli, D.; Zanardi, C.; Pellati, F.
abstract

Cannabis sativa L. is a plant known all over the world, due to its history, bioactivity and also social impact. It is chemically complex with an astonishing ability in the biosynthesis of many secondary metabolites belonging to different chemical classes. Among them, cannabinoids are the most investigated ones, given their pharmacological relevance. In order to monitor the composition of the plant material and ensure the efficacy and safety of its derived products, extraction and analysis of cannabinoids play a crucial role. In this context, in addition to a conventional separation method based on HPLC with UV/DAD detection, a new strategy based on a non-separation procedure, such as 13C-qNMR, may offer several advantages, such as reduced solvent consumption and simultaneous acquisition of the quali/quantitative data related to many analytes. In the light of all the above, the aim of this work is to compare the efficiency of the above-mentioned analytical techniques for the study of the main cannabinoids in different samples of cannabis inflorescences, belonging to fibre-type, recreational and medical varieties. The 13C-qNMR method here proposed for the first time for the quantification of both psychoactive and non-psychoactive cannabinoids in different cannabis varieties provided reliable results in comparison to the more common and consolidated HPLC technique.


2020 - A community-built calibration system: The case study of quantification of metabolites in grape juice by qNMR spectroscopy [Articolo su rivista]
Musio, B.; Ragone, R.; Todisco, S.; Rizzuti, A.; Latronico, M.; Mastrorilli, P.; Pontrelli, S.; Intini, N.; Scapicchio, P.; Triggiani, M.; Di Noia, T.; Acquotti, D.; Airoldi, C.; Assfalg, M.; Barge, A.; Bateman, L.; Benevelli, F.; Bertelli, D.; Bertocchi, F.; Bieliauskas, A.; Borioni, A.; Caligiani, A.; Callone, E.; Camra, A.; Cesare Marincola, F.; Chalasani, D.; Consonni, R.; Dambruoso, P.; Davalli, S.; David, T.; Diehl, B.; Donarski, J.; Gil, A. M.; Gobetto, R.; Goldoni, L.; Hamon, E.; Harwood, J. S.; Kobrlova, A.; Longobardi, F.; Luisi, R.; Mallamace, D.; Mammi, S.; Martin-Biran, M.; Mazzei, P.; Mele, A.; Milone, S.; Molero Vilchez, D.; Mulder, R. J.; Napoli, C.; Ragno, D.; Randazzo, A.; Rossi, M. C.; Rotondo, A.; Sackus, A.; Saez Barajas, E.; Schievano, E.; Sitaram, B.; Stevanato, L.; Takis, P. G.; Teipel, J.; Thomas, F.; Torregiani, E.; Valensin, D.; Veronesi, M.; Warren, J.; Wist, J.; Zailer-Hafer, E.; Zuccaccia, C.; Gallo, V.
abstract

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.


2020 - Innovative methods for the preparation of medical Cannabis oils with a high content of both cannabinoids and terpenes [Articolo su rivista]
Ternelli, M.; Brighenti, V.; Anceschi, L.; Poto, M.; Bertelli, D; Licata, M.; Pellati, F.
abstract

Cannabis-based medications are being increasingly used for the treatment of different clinical conditions. Among all galenic formulations, olive oil extracts from medical Cannabis are the most prescribed ones for their easy preparation and usage. A great variety of methods have been described so far for the extraction of medical Cannabis oils to reach a high yield of Δ9-tetrahydrocannabinol (Δ9-THC), but poor attention has been paid to the preservation of the terpene fraction from the plant, which may contribute to the overall bioactivity of the extracts. In this context, the present study was aimed at the chemical characterization of different medical Cannabis oils prepared by following both innovative and existing extraction protocols, with particular attention to cannabinoids and terpenes, in order to set up a suitable method to obtain an extract rich in these chemical classes. In particular, six different extraction procedures were followed, based on different techniques, of which all but one included a decarboxylation of the plant material. The profile of cannabinoids was studied in detail by means of HPLC-ESI-MS/MS, while terpenes were characterized by means both GC-MS and GC-FID techniques coupled with solid-phase microextraction operated in the head-space mode (HS-SPME). An innovative method that is based on the extraction of the oil by dynamic maceration at room temperature from plant inflorescences, which were partially decarboxylated in a closed system at a moderate temperature and partially pre-extracted with ethanol, produced similar yields of bioactive compounds as that obtained by using a microwave-assisted distillation of the essential oil from the plant material, in combination with a maceration extraction of the oil from the residue. Both these new methods provided a higher efficiency over already existing extraction procedures of medical Cannabis oils and they can be applied to obtain a product with a high therapeutic value.


2020 - New insights into bioactive compounds from the medicinal plant Spathodea campanulata P. Beauv. and their activity against Helicobacter pylori [Articolo su rivista]
Ngnameko, C. R.; Marchetti, L.; Zambelli, B.; Quotadamo, A.; Roncarati, D.; Bertelli, D.; Njayou, F. N.; Smith, S. I.; Moundipa, P. F.; Costi, M. P.; Pellati, F.
abstract

The medicinal plant Spathodea campanulata P. Beauv. (Bignoniaceae) has been traditionally applied for the prevention and treatment of diseases of the kidney and urinary system, the skin, the gastrointestinal tract, and inflammation in general. The present work shows for the first time how chemical components from this plant inhibit Helicobacter pylori growth by urease inhibition and modulation of virulence factors. The crude extract and the main fractions of S. campanulata bark were tested on H. pylori isolated strains and the active ones were further fractionated. Fractions and sub-fractions of the plant crude extract were characterized by ultra-high-performance liquid chromatographic tandem high resolution-mass spectrometry detection (UHPLC-HRMS). Several phenolics and triterpenoids were identified. Among the sub-fractions obtained, SB2 showed the capacity to inhibit H. pylori urease in a heterologous bacterial model. One additional sub-fraction (SE3) was able to simultaneously modulate the expression of two adhesins (HopZ and BabA) and one cytotoxin (CagA). The flavonol kaempferol was identified as the most interesting compound that deserves further investigation as a new hit for its capacity to modulate H. pylori virulence factors.


2019 - Advanced characterization technique for wine [Poster]
Setti, Leonardo; Minguillón, Cristina; Montevecchi, Giuseppe; Masino, Francesca; Bertelli, Davide; Antonelli, Andrea
abstract


2019 - Autenticazione degli alimenti [Capitolo/Saggio]
Bertelli, Davide; Lidia Bonaccorsi, Ivana; Dugo, Paola; Plessi, Maria
abstract

Il capitolo si occupa delle problematiche legate all'assicurazione della autenticità degli alimenti descrivendo brevemente le più moderne tecniche analitiche a disposizione del chimico


2019 - Development of a new method for the analysis of cannabinoids in honey by means of high-performance liquid chromatography coupled with electrospray ionisation-tandem mass spectrometry detection [Articolo su rivista]
Brighenti, V.; Licata, M.; Pedrazzi, T.; Maran, D.; Bertelli, D.; Pellati, F.; Benvenuti, S.
abstract

Fibre-type Cannabis sativa L. (hemp) represents a valuable resource in many different fields, including both the pharmaceutical and food ones. This plant contains non-psychoactive cannabinoids, a class of bioactive compounds biosynthesized in both female and male inflorescences. Among them, cannabidiol (CBD) is the most interesting compound from a medicinal point of view. Indeed, several scientific studies have proved its therapeutic potential in a large number of pathologies, in addition to its biological effects attributable to its antioxidant, neuroprotective and anti-inflammatory properties. The analysis of the amount of cannabinoids in food and food supplements represents a critical issue in the ambit of both the quality assurance and the dietary intake control of these biologically active compounds. In this ambit, a particular attention is necessary for apiary products, since they are widely consumed and they can be produced by bees starting from different floral sources. In the light of all the above, the aim of this study was to develop for the first time a new analytical method based on RP-HPLC with ESI-MS/MS detection for the determination of CBD and related cannabinoids in honey. A quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction procedure with an un-buffered method was selected and optimised as the more suitable protocol. As regards detection, it was carried out by using a linear ion trap quadrupole (QTRAP) mass analyser, operated in the multiple reaction monitoring (MRM) mode. Hemp male inflorescences and pollen were analysed in parallel by means of HPLC-UV/DAD, since bees can transfer pollen into their hives and, consequently, into beehive products. The method developed and validated for the first time in this work was finally applied to the analysis of cannabinoids in honey samples, thus demonstrating to be a useful tool for both quality control and safety assurance.


2019 - Identification and determination of bioactive phenylpropanoid glycosides of Aloysia polystachya (Griseb. et Moldenke) by HPLC-MS [Articolo su rivista]
Marchetti, Lucia; Pellati, Federica; Graziosi, Riccardo; Brighenti, Virginia; Pinetti, Diego; Bertelli, Davide
abstract

Aloysia polystachya (Griseb. et Moldenke) has not been deeply investigated in past years and currently data about its chemical composition are limited. Phenolic compounds characterization can be very difficult in vegetable matrices, owing to bonds to sugar moieties or conjugation, giving rise to complex structures. In this work, methanolic extracts of Aloysia polystachya leaves were analyzed by HPLC-ESI-MS, the favourite technique for the separation and quantification of their polyphenols. To assess the complete characterization and quantification of the phenylpropanoid fraction, three different MS techniques have been coupled to HPLC: ion trap mass spectrometry (Ion Trap LC/MS), quadrupole-time of flight high resolution mass spectrometry (Q-TOF HRMS) and triple-quadrupole (TQ LC/MS) for the quantification. Eleven phenylpropanoid glycosides were identified and quantified and, among them, the compounds forsythoside A, plantainoside C, purpureaside D, martynoside and its two isomers were detected for the first time to the best of our knowledge. The results presented here could be helpful to assess the quality of this plant and could further contribute to the chemotaxonomy of the genus.


2019 - Moretta di Vignola, da nicchia ad alimento funzionale [Articolo su rivista]
Bertelli, Davide; Marchetti, Lucia; Plessi, Maria; Soragni, Fabrizia; Bellelli, S.; Bergonzoni, L.; Dondini, L.; Grandi, M.; Venturi, Silvia; Etiopi, C.; Monari, W.; DE BERNARDI, Alberto; Quartieri, G.; Lugli, S.
abstract

L'aricolo riporta i primi risultati del progetto di ricerca finanziato da Fondazione Vignola e Comune di vignola per la caratterizzazione chimica e funzionale e valorizzazione della Ciliegia "Moretta di Vignola"


2019 - Standard methods for Apis mellifera propolis research [Articolo su rivista]
Bankova, Vassya; Bertelli, Davide; Borba, Renata; Conti, Josè; Barbosa da Silva Cunha, Ildenize; Danert, Carolina; Eberlin, Marcos; Falcão, Soraja; Isla, Maria; Nieva Moreno, Maria; Papotti, Giulia; Popova, Milema; Santiago, Karina; Salas, Anna; Sawaya, Helena; Schwab, Nicolas; Sforcin, Joseè; Simone Finstrom, Michael; Spivak, Spivak; Trusheva, Borjana; Vilas Boas, Miguel; Wilson, Michael; Zampini, Catiana
abstract

Propolis is one of the most fascinating honey bee (Apis mellifera L.) products. It is a plant derived product that bees produce from resins that they collect from different plant organs and with which they mix beeswax. Propolis is a building material and a protective agent in the bee hive. It also plays an important role in honey bee social immunity, and is widely used by humans as an ingredient of nutraceuticals, over-the-counter preparations and cosmetics. Its chemical composition varies by geographic location, climatic zone and local flora. The understanding of the chemical diversity of propolis is very important in propolis research. In this manuscript, we give an overview of the available methods for studying propolis in different aspects: propolis in the bee colony; chemical composition and plant sources of propolis; biological activity of propolis with respect to bees and humans; and approaches for standardization and quality control for the purposes of industrial application.


2019 - Use of 1H NMR to detect the percentage of pure fruit juices in blends [Articolo su rivista]
Marchetti, L.; Pellati, F.; Benvenuti, S.; Bertelli, D.
abstract

The consumption of high-nutritional-value juice blends is increasing worldwide and, considering the large market volume, fraud and adulteration represent an ongoing problem. Therefore, advanced anti-fraud tools are needed. This study aims to verify the potential of 1H NMR combined with partial least squares regression (PLS) to determine the relative percentage of pure fruit juices in commercial blends. Apple, orange, pineapple, and pomegranate juices were selected to set up an experimental plan and then mixed in different proportions according to a central composite design (CCD). NOESY (nuclear Overhauser enhancement spectroscopy) experiments that suppress the water signal were used. Considering the high complexity of the spectra, it was necessary to pretreat and then analyze by chemometric tools the large amount of information contained in the raw data. PLS analysis was performed using venetian-blind internal cross-validation, and the model was established using different chemometric indicators (RMSEC, RMSECV, RMSEP, R2CAL, R2CV, R2PRED). PLS produced the best model, using five factors explaining 94.51 and 88.62% of the total variance in X and Y, respectively. The present work shows the feasibility and advantages of using 1H NMR spectral data in combination with multivariate analysis to develop and optimize calibration models potentially useful for detecting fruit juice adulteration.


2019 - Use of 13C-qNMR Spectroscopy for the Analysis of Non-Psychoactive Cannabinoids in Fibre-Type Cannabis sativa L. (Hemp) [Articolo su rivista]
Marchetti, L.; Brighenti, V.; Rossi, M. C.; Sperlea, J.; Pellati, F.; Bertelli, D.
abstract

Cannabis sativa L. is a dioecious plant belonging to the Cannabaceae family. The discovery of the presence of many biologically-active metabolites (cannabinoids) in fibre-type Cannabis (hemp) has recently given rise to the valorisation of this variety. In this context, the present study was aimed at the multi-component analysis and determination of the main non-psychoactive cannabinoids (cannabidiol, cannabidiolic acid, cannabigerol and cannabigerolic acid) in female inflorescences of different hemp varieties by means of 13C quantitative nuclear magnetic resonance spectroscopy (qNMR). The method proposed here for the first time for the determination of cannabinoids provided reliable results in a competitive time with respect to the more consolidated HPLC technique. In fact, it gave sufficiently precise and sensitive results, with LOQ values lower than 750 µg/mL, which is easily achievable with concentrated extracts, without affecting the quality of 13C-qNMR spectra. In conclusion, this method can be considered as a promising and appropriate tool for the comprehensive chemical analysis of bioactive cannabinoids in hemp and other derived products in order to ensure their quality, efficacy and safety.


2018 - Analytical methods for the study of bioactive compounds from medicinally used Echinacea species [Articolo su rivista]
Bruni, R.; Brighenti, V.; Caesar, L. K.; Bertelli, D.; Cech, N. B.; Pellati, F.
abstract

Echinacea purpurea (L.) Moench, Echinacea angustifolia DC. var. angustifolia and Echinacea pallida (Nutt.) Nutt. are frequently used as medicinal plants and their preparations are among the most widely used herbal medicines. The extracts from these species have shown a highly complex chemical composition, including polar compounds (caffeic acid derivatives, CADs), non-polar compounds (alkylamides and acetylenic secondary metabolites; essential oil) and high molecular weight constituents (polysaccharides and glycoproteins). All these chemical classes of compounds have demonstrated to possess interesting biological activities. In the light of all the above, this paper is focused on the analytical techniques, including sample preparation tools and chromatographic procedures, for the chemical analysis of bioactive compounds in medicinally used Echinacea species. Since sample preparation is considered to be a crucial step in the development of analytical methods for the determination of constituents present in herbal preparations, the strength and weakness of different extraction techniques are discussed. As regards the analysis of compounds present in Echinacea plant material and derivatives, the application of different techniques, mainly HPLC, HPLC-ESI-MS, HPLC-ESI-MS/MS, HPCE, HPTLC and GC, is discussed in detail. The strength, weakness and applicability of the different separation tools are stated.


2018 - Chemical composition of Italian propolis of different ecoregional origin [Articolo su rivista]
Gardini, Silvia; Bertelli, Davide; Marchetti, Lucia; Graziosi, Riccardo; Pinetti, Diego; Plessi, Maria; Luigi Marcazzan, Gian
abstract

The aim of this work was studying and identifying the main physicochemical properties and active constituents in Italian propolis derived from resident hives throughout the peninsula. The data, potentially useful to establish important propolis quality criteria, were compared to those typical of poplar type propolis and used to build a classification model to link the propolis characteristics to its ecoregion of origin. HPLC-ESI-TQ MS was used to quantify twenty-one phenolic compounds in propolis extracts. Considering the bioactive substances and the antioxidant activity, statistically significant characteristics can distinguish propolis from the considered Italian ecoregions: Mediterranean and temperate division and, due to the high presence of poplar trees, the Po plain province as part of temperate division. Chrysin is the most abundant flavonoid in all the samples followed by galangin and pinocembrin. Regarding phenolic acids the samples from temperate and Mediterranean ecoregions are characterized by high amount of ferulic and isoferulic acids.


2018 - Determinaion of 1-deoxynojirimicin (DNJ) in mulberry leaves (Morus app. L.), silkworms and silk by HPLC-TQ-MS [Abstract in Atti di Convegno]
Marchetti, Lucia; Cappellozza, Silvia; Saviane, Alessio; Bertelli, Davide
abstract

Introduction DNJ is a constituent of mulberry leaves and when consumed as part of the diet it showed beneficial properties on health: suppression of high blood glucose levels, antibacterial and antiviral activities [1,2]. In this work DNJ content in different matrices was investigated, the importance lies in the potential uses of these products as food and feed, nutraceutical and medical device. Methods Twenty-nine samples of mulberry leaves from an experimental field (CREA-Padova), silk worms larvae and silk cocoons were analyzed by HILIC technique. EtOH:H2O 50% solution and water 60° were employed for leaves extraction. Grinded cocoons and freeze-dried larvae were extracted with EtOH:H2O 50% (at 60°C for cocoons). The detection was performed by using ESI in positive ion MRM mode. Results The optimized mass conditions allowed the identification of three usable transitions (one for the quantification of DNJ 164.1146.1, others as qualifier ions 164.1128.1, 164.1110.1). DNJ was detected in all the considered matrices and determined by using its calibration curve (r2=0.9865). In the case of leaves, water infusion resulted less efficient with respect to EtOH:H2O extraction. The mean concentration value in leaves obtained with infusion is 0.073±0.004 mg/g while 2.56±0.3 mg/g for extracts. The mean concentration recovered in larvae is 0.034±0.001 mg/g whereas substantially lower amounts were obtained for silk (3.12*10-5 mg/g). Conclusions In this work an efficient HPLC-TQ-MS method was applied to the determination of DNJ in leaves, larvae and silk. The study showed that Morus nigra L. presents the highest content among the tested species and that DNJ is detectable also in larvae and silk. These results could be useful in the further development of herbal supplements and for the potential use of larvae as medicated feed or functional food.


2018 - New methods for the comprehensive analysis of bioactive compounds in Cannabis sativa L. (hemp) [Articolo su rivista]
Pellati, F.; Brighenti, V.; Sperlea, J.; Marchetti, L.; Bertelli, D.; Benvenuti, S.
abstract

Cannabis sativa L. is a dioecious plant belonging to the Cannabaceae family. The main phytochemicals that are found in this plant are represented by cannabinoids, flavones, and terpenes. Some biological activities of cannabinoids are known to be enhanced by the presence of terpenes and flavonoids in the extracts, due to a synergistic action. In the light of all the above, the present study was aimed at the multi-component analysis of the bioactive compounds present in fibre-type C. sativa (hemp) inflorescences of different varieties by means of innovative HPLC and GC methods. In particular, the profiling of non-psychoactive cannabinoids was carried out by means of HPLC-UV/DAD, ESI-MS, and MS2. The content of prenylated flavones in hemp extracts, including cannflavins A and B, was also evaluated by HPLC. The study on Cannabis volatile compounds was performed by developing a new method based on headspace solid-phase microextraction (HS-SPME) coupled with GC-MS and GC-FID. Cannabidiolic acid (CBDA) and cannabidiol (CBD) were found to be the most abundant cannabinoids in the hemp samples analysed, while ß-myrcene and ß-caryophyllene were the major terpenes. As regards flavonoids, cannflavin A was observed to be the main compound in almost all the samples. The methods developed in this work are suitable for the comprehensive chemical analysis of both hemp plant material and related pharmaceutical or nutraceutical products in order to ensure their quality, efficacy, and safety.


2018 - Nuclear magnetic resonance and high-performance liquid chromatography techniques for the characterization of bioactive compounds from Humulus lupulus L. (hop) [Articolo su rivista]
Bertelli, D.; Brighenti, V.; Marchetti, L.; Reik, A.; Pellati, F.
abstract

Humulus lupulus L. (hop) represents one of the most cultivated crops, it being a key ingredient in the brewing process. Many health-related properties have been described for hop extracts, making this plant gain more interest in the field of pharmaceutical and nutraceutical research. Among the analytical tools available for the phytochemical characterization of plant extracts, quantitative nuclear magnetic resonance (qNMR) represents a new and powerful technique. In this ambit, the present study was aimed at the development of a new, simple, and efficient qNMR method for the metabolite fingerprinting of bioactive compounds in hop cones, taking advantage of the novel ERETIC 2 tool. To the best of our knowledge, this is the first attempt to apply this method to complex matrices of natural origin, such as hop extracts. The qNMR method set up in this study was applied to the quantification of both prenylflavonoids and bitter acids in eight hop cultivars. The performance of this analytical method was compared with that of HPLC-UV/DAD, which represents the most frequently used technique in the field of natural product analysis. The quantitative data obtained for hop samples by means of the two aforementioned techniques highlighted that the amount of bioactive compounds was slightly higher when qNMR was applied, although the order of magnitude of the values was the same. The accuracy of qNMR was comparable to that of the chromatographic method, thus proving to be a reliable tool for the analysis of these secondary metabolites in hop extracts.


2018 - Simultaneous determination of glicine max L. and lupulus humulus L. active principles in dietary supplement [Abstract in Atti di Convegno]
Marchetti, Lucia; Bertelli, Davide
abstract

Introduction Soy isoflavones and hop prenylflavonoids are the most effective natural substances against menopausal symptomatology and are used in herbal supplements [1]. Nowadays the easy recourse to supplements is of immediate concern for overdoses and side effects, moreover, these products are more exposed than drugs to the risk of adulteration. Novel analytical approaches for quality control are necessary. Methods Methanolic extracts of hop and soy supplements were evaporated and dissolved in DMSOd6. NMR analysis was carried out with a Bruker Avance III HD600 MHz spectrometer equipped with CryoProbe BBO H&F 5mm. The most resolved peaks in the aromatic area were assigned to the main compounds using 2D sequences. Daidzein, genistein, glicitein and xanthohumol were determined by Bruker-ERETIC2 technique. Results High quality spectra were obtained with signal to noise ratio largely over the limit required for the quantification of the main compounds of interest. 7 out of the 8 analysed samples actually presented content of active principles which differ from the declared value more than 10%. In particular, 5 samples presented lower amounts while the remaining 2 showed higher quantities with respect to the value reported on the label. In the former case the therapeutic dose will not be reached when the product is administered. In the latter instead, the greater risk is to exceed the maximum recommended dose. Conclusions qNMR in the ambit of complex mixtures analysis has proved to be promising and advantageous, allowing the simultaneous determination in a single experiment, of many molecules also structurally different from one another and avoiding time consuming sample purification steps also reducing the production of artefacts.


2017 - Novel 2D-NMR Approach for the Classification of Balsamic Vinegars of Modena [Articolo su rivista]
Graziosi, Riccardo; Bertelli, Davide; Marchetti, Lucia; Papotti, Giulia; Rossi, Maria Cecilia; Plessi, Maria
abstract

The aim of this work is to evaluate the possibility of using 2D-NMR for the construction of classification models for balsamic vinegars of Modena. The goal was to obtain an indirect indicator of authenticity and a quality control tool. The spectral data were analyzed by chemometric methods, aiming to discriminate the samples in relation to their origin. Application of general discriminant analysis (GDA) revealed a good discrimination; the two obtained models explained 83.9% and 97.3% of the total variance with a predictive capacity of 98.6% and 98.4%, respectively. The signals of 5-HMF, β-glucose, 2,3-butanediol, 6- acetyl glucose, and different aliphatic signals of sugars were the most significant variables. These results are very promising for giving an important contribution in quality control and characterization of such very valuable foods.


2017 - Study of white tea nutraceutical properties [Abstract in Atti di Convegno]
Papetti, Adele; Robustelli della Cuna, F.; Boselli, C.; Tava, A.; Bertelli, Davide; Marchetti, Lucia; Maietti, Annalisa; Tedeschi, Paola
abstract

Tea is a widely consumed beverage in the world and its consumption is highly recommended due to the great number of healthy properties. Tea can be classified in white, green, oolong, and black according to the different processing method. White tea, a rare variety, is little fermented, only made by new growth buds and young leaves, and after picking is immediately dried to maintain its delicate and sweet taste. Recently, many health benefits including anti-oxidative, anti-inflammatory, anti-melanogenic properties, an effect on prediabetesinduced reproductive dysfunction and on the stabilization of collagen in dentine resulting in functional remineralization have been attributed to white tea. Due to these functional properties, it could be interesting define the nutraceutical properties of white tea consisting of only sprouting buds or sprouting buds with the first three leaves grown according to minimum processing system. The aim of the present research is to investigate samples, commercially available in Europe, coming from four countries: China (Camellia sinensis var. sinensis), India, Sri Lanka, and Malawi (Camellia sinensis var. assamica), for the chemical composition and minerals profile of the different white tea infusions (consisted both of only buds or of buds plus young leaves). The chemical composition has been defined by LC-ESI-MSn and mono and two dimentional High Resolution NMR spectroscopy; furthermore, a quantitative profile of the main components has been investigated by a RP-HPLC-DAD method and tentatively by quantitative NMR using ERETIC 2 method. For each sample, macro and trace elements were determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES), and ICP-mass spectrometry (MS). For the first time, a differentiation of nutraceutical properties between white tea buds and buds plus young leaves from different countries will be defined.


2016 - DETERMINATION OF SOY ISOFLAVONES IN FOOD SUPPLEMENTS BY 1H-qNMR [Abstract in Atti di Convegno]
Bertelli, Davide; Graziosi, Riccardo; Belli, Silvia; Plessi, Maria
abstract

Isoflavones are a class of compounds with estrogenic activity and they are found in small amounts in a number of legumes, grains, and vegetables, but soybeans are by far the most concentrated source of isoflavones in the human diet. Soy products that are gaining popularity in Western countries include soy-based meat substitutes, soy milk, soy cheese, and yogurt and many different food supplements, in which, soy extracts may be present alone or in association with others natural compounds. Soy isoflavone extracts are available as dietary supplements without a prescription in the majority of countries and also in Italy. These products are not usually standardized, and the amounts of isoflavones they provide may vary considerably. Moreover, quality control may be an issue with some of these products [1]. When isoflavone supplements were tested for their isoflavone content, the isoflavone content in the product differed by more than 10% from the amount claimed on the label in approximately 50% of the products tested [2]. For this reason 1H NMR spectra of different methanolic extracts of soy-based food supplements were recorded using a Bruker FT-NMR AVANCE III HD 600 MHz spectrometer. It was possible to identify signals belonging to the soy isoflavones in the aromatic zone (from 6.5 to 8.5 ppm). Genistein, daidzein and glycitein signals were assigned also using 13C, JRes and heteronuclear experiments such as HSQC and HMQC. The identified compounds were tentatively quantified using ERETIC 2 method. The obtained results further demonstrate the potential of the NMR technique in food chemistry.


2016 - Identification and quantification of phenylpropanoid glycosides in Aloysia polystachya (Griseb and Moldenke) by HPLC-TQMS [Abstract in Atti di Convegno]
Bertelli, Davide; Graziosi, Riccardo; Plessi, Maria
abstract

Data on the chemical composition of Aloysia polystachya (Griseb. et Moldenke) are poor in the literature. It is an herbaceus plant, widely distributed in subtropical regions of South America where it is commonly known as “tè burro”. It is widely used as a dietary supplement or tea substitute and in folk medicine. Phenolic compounds characterization in plant matrix can be very difficult, owing to the bonding to different sugar moieties, or conjugation to form complex structures. Among the different methods available, high-performance liquid chromatography (HPLC) is preferable for the separation and quantification of polyphenolics. In present work the HPLC-MS characterization and quantification of the phenylpropanoid glycosides fraction, purified by Solid Phase Extraction (SPE), of Aloysia polystachya (Griseb. et Moldenke) extracts was performed. Three different MS techniques have been coupled to HPLC, to identify and quantify the compounds present in the extracts: ion trap mass spectrometry (Ion Trap LC/MS), and the quadrupole-time of flight high resolution mass spectrometry (Q-TOF HRMS) for the identification and HPLC-TQMS in MRM mode for the quantification, using verbascoside as reference standard. Nine phenylpropanoid glycosides were identified and quantified after SPME purification of methanolic extract of Aloysia polystachya leaves. Among them, the compounds forsythoside A, plantainoside C, purpureaside D, martynoside and its two isomers were identified here for the first time. The content of phenylpropanoid glycosides ranges from 3.3 mg/g for verbascoside to 0.08 mg/g for purpureaside D. The results present here could be helpful to assess the quality of Aloysia polystachya leaves. Knowledge of the content of phenylpropanoid glycosides could further contribute to the chemotaxonomy of the genus.


2016 - Identification of phenylpropanoid glycosides from Aloysia polystachya (Griseb. et Moldenke) by HPLC-MS analysis [Abstract in Rivista]
Bertelli, Davide; Graziosi, Riccardo; Plessi, Maria
abstract

Introduction Data on the chemical composition of Aloysia polystachya (Griseb. et Moldenke) are poor in the literature. Phenolic compounds characterization in plant matrix can be very difficult, owing to bond to different sugar moieties, or conjugation to form complex structures. Despite a great number of investigations, also the separation and the simultaneous determination of polyphenolics of different groups remain difficult. Among the different methods available, high-performance liquid chromatography (HPLC) is preferable for the separation and quantification of polyphenolics. The HPLC-MS characterization of the phenylpropanoid glycosides fraction, purified by Solid Phase Extraction (SPE), in Aloysia polystachya (Griseb. et Moldenke) extract was performed. Method Two different MS techniques have been coupled to HPLC, to identify the compounds present in the extract, and support tentative structure identification: ion trap mass spectrometry (Ion Trap LC/MS), and the quadrupole-time of flight high resolution mass spectrometry (Q-TOF HRMS). Results / Discussion / Conclusion Nine phenylpropanoid glycosides were identified in methanolic extract of the Aloysia polystachya (Griseb. et Moldenke) leaves. Among them, the compounds forsythoside A, plantainoside C, purpureaside D, martynoside and its two isomers were identified here for the first time. The results present here could be helpful in the future developing and validating of an analytical method to quantify the isolated compounds, and to assess the quality of Aloysia polystachya (Griseb. et Moldenke) leaves. Knowledge of the content of phenylpropanoid glycosides could further contribute to the chemotaxonomy of the genus.


2016 - In vitro bioaccessibility, transepithelial transport and antioxidant activity of Urtica dioica L. phenolic compounds in nettle based food products [Articolo su rivista]
Bonetti, Gianpiero; Tedeschi, Paola; Meca, Giuseppe; Bertelli, Davide; Manes Jordi, Damon; Brandolini, Vincenzo; Maietti, Annalisa; Manes,
abstract

Nettle (Urtica dioica L.) is a well-known plant with a wide historical background use of stems, roots and leaves. Nettle leaves are an excellent source of phenolic compounds, principally 3-caffeoylquinic acid (3-CQA), caffeoylmalic acid (CMA) and rutin. The aim of this work was to evaluate the bioaccessibility (BAC), the bioavailability (BAV) and the antioxidant activity of nettle phenolic compounds present in foods and supplements. The BAC of nettle phenolics was evaluated with an in vitro dynamic digestion of real food matrices: the type of food matrix and chemical characteristic affected the kinetics of release and solubilization, with the highest BAC after duodenal digestion. A study of duodenal trans epithelial transport evidenced low bioavailability of native forms of 3-CQA, CMA and rutin. Simulation of colonic metabolism confirmed that phenolic compounds are fermented by gut microflora, confirming the need for further investigations on the impact of phenolic compounds at the large intestine level. Photochemiluminescence assay of the simulated digestion fluids demonstrated that ingestion of Urtica based foods contributes to create an antioxidant environment against superoxide anion radicals in the entire gastrointestinal tract (GIT).


2016 - Usefulness of 1H-NMR in the study of the bioactive compounds of Hop (Humulus Lupulus L.) [Abstract in Atti di Convegno]
Bertelli, Davide; Graziosi, Riccardo; Marchetti, Lucia; Plessi, Maria
abstract

The cultivation of the hop plant (Humulus lupulus L.) has a long history. Since ancient times, hop have been used in folk medicine for its claimed anti-inflammatory, antiseptic, antidiuretic, (an)aphrodisiac, hypnotic, sedative, and stomachic properties. Moreover it is one of the main ingredients used in brewing. Today, a wide range of over-the-counter preparations containing hop extracts or hop-derived products is available on the market, in particular for use in the phytotherapy of sleep disorders or pain relief and in postmenopausal therapy [1]. Moreover it is demonstrated that moderate beer drinking can be good for health and for the prevention of different chronic diseases [2]. Much of attention is addressed to the polyphenolic content, and specific compounds, such as xanthohumol and 8-prenylnaringenin, have been identified as multipotent bioactive compounds. Moreover, increasing evidence reveals that the so-called hop bitter acids, which represent up to 30% of the total bitter-tasting compounds of hops, exhibit interesting effects on human health. In the present work, we focused on this group of hop secondary metabolites and evaluated the usefulness of 1H-NMR in performing a phytochemical characterization of the main hop compounds. For this reason 1H NMR spectra of different extracts of hop were recorded using a Bruker FT-NMR AVANCE III HD 600 MHz spectrometer. It was possible to identify signals belonging to the main components of hop in the regions ranging between 6.5 to 8.5 ppm and 1.5 to 3 ppm, using 13C, JRes and heteronuclear experiments such as HSQC and HMQC. The identified compounds were tentatively quantified using ERETIC 2 tool. This tool is based on PULCON method which is based on the principle of reciprocity which indicates that le length of a 90° degrees pulse is inversely proportional to the NMR signal intensity. Pyridoxine hydrochloride was selected as external standard compound and the quantification was performed using a simple non- presaturated 1H-NMR sequence. The obtained results further demonstrate the potential of the NMR technique in the characterization of health beneficial compounds from natural sources.


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 - Antioxidant activity, phenolic compounds, and NMR characterization of Balsamic and Traditional Balsamic Vinegar of Modena [Articolo su rivista]
Bertelli, Davide; Maietti, Annalisa; Papotti, Giulia; Tedeschi, Paola; Bonetti, Gianpiero; Graziosi, Riccardo; Brandolini, Vincenzo; Plessi, Maria
abstract

The aim of this work is to study the chemical and functional characterization of balsamic vinegar of Modena (BVM) and traditional balsamic vinegars from Modena (TBVM), using different methods to assay the phenolic content and the antioxidant activity. Besides, NMR analysis was used to obtain information about the principal substances in the samples. One hundred and nine samples of both TBVM and BVM were analyzed in all. Despite the observed high intragroup variability, the statistical analysis showed statistically significant differences between TBVM and BVM. The TBVMs are richer in phenolics, flavonoids, and tannins and show higher antioxidant capacity than BVMs. The general discriminant analysis (GDA) model including all the compositional and NMR data was able to group the samples according to the type of vinegar. The first canonical discriminant function explains 92.2 % of the total variance, and the leave-one out cross-validation show a predictive capacity of 89.6 %


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

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


2015 - Traditional balsamic vinegar and balsamic vinegar of Modena analyzed by nuclear magnetic resonance spectroscopy coupled with multivariate data analysis [Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; Graziosi, Riccardo; Maietti, Annalisa; Tedeschi, Paola; Marchetti, Andrea; Plessi, Maria
abstract

Balsamic vinegar of Modena (BVM) and traditional balsamic vinegar of Modena (TBVM) are highly appreciated typical Italian products. The quality control and authentication assurance of both these balsamic vinegars are very important topics. In the recent years, the interest to develop new and standardized analytical procedures, able to further enhance the quality and commercial value of these typical and unique products and to preserve them from possible sophistications and adulterations, is increased. In this work, 76 samples of both BVM and TBVM were analized by 1H NMR spectroscopy coupled with multivariate data analysis. The spectral data were analyzed by principal component analysis (PCA), general discriminant analysis (GDA) and classification tree analysis (CTA). The best and very promising model was obtained by a GDA which shows 98.6% of total variance explained by the first canonical function and a predictive capacity of 98.4% with a good separation between clusters. The signals of 5-HMF, -glucopyranose, malic acid, succinic and acetic acids and a signal at 3.3 ppm referred to the glucose and fructose region were found to be the most statistically significant variables.


2014 - A mid level data fusion strategy for the Varietal Classification of Lambrusco PDO wines [Articolo su rivista]
Silvestri, Michele; Elia, Andrea; Bertelli, Davide; Salvatore, Elisa; Durante, Caterina; Li Vigni, Mario; Marchetti, Andrea; Cocchi, Marina
abstract

Nowadays the necessity to reveal the hidden information from complex data sets is increasing due to the development of high-throughput instrumentation. The possibility to jointly analyze data sets arising from different sources (e.g. different analytical determinations/platforms) allows capturing the latent information that would not be extracted by the individual analysis of each block of data. Several approaches are proposed in the literature and are generally referred to as data fusion approaches. In this work a mid level data fusion is proposed for the characterization of three varieties (Salamino di Santa Croce, Grasparossa di Castelvetro, Sorbara) of Lambrusco wine, a typical PDO wine of the district of Modena (Italy). Wine samples of the three different varieties were analyzed by means of 1H-NMR spectroscopy, Emission-Excitation Fluorescence Spectroscopy and HPLC-DAD of the phenolic compounds. Since the analytical outputs are characterized by different dimensionalities (matrix and tensor), several multivariate analyses were applied (PCA, PARAFAC, MCR-ALS) in order to extract and merge, in a hierarchical way, the information present in each data set. The results showed that this approach was able to well characterize Lambrusco samples giving also the possibility to understand the correlation between the sources of information arising from the three analytical techniques.


2014 - Analytical traceability of Reggio Emilia watermelon [Relazione in Atti di Convegno]
Maietti, A.; Bertelli, Davide; Tedeschi, P.; Papotti, Giulia; Bonetti, G.; Brandolini, V.
abstract

The consumer’s demand for the quality and safety fresh fruits and vegetables has been increasing due to the ease of intake and nutritional benefits. Epidemiological studies have correlated the consumption of bioactive ingredients with declining the incidence of several physiological threats. It is known that the amount of each compounds in fruits and vegetables have a significant impact on the quality of the product and it’s strongly influenced by genotype differences and external factors such as agro-technical processes, environmental conditions, ripening degree at harvest and post harvest manipulation. Watermelon consumption helps to regulate acid-base equilibrium, removes/lowers the cholesterol level, has strong diuretic tendencies (removes excess water from the body, contribute to clearing the kidneys/prevents the formation of bladder stones, kidney stones among others. It is an important source of potassium and many micronutrients. The aim of the present research was the chemotyping of watermelon of Reggio Emilia. The Reggio Emilia district has always been suited for the watermelon’s cultivation and the Reggio Emilia’s watermelon quality was identified in the soil characteristics and the highly specialized producers. The research project has been developed in three years and was finalized to obtain the IGP certification. The variation of proximate composition (proteins, brix degree, mineral content), minor secondary bioactive compounds (ascorbic acid, carotenoids, polyphenols) and antioxidant capacity was evaluated in relation to soil composition, genotype (var. Myiako, Topgun, Sentinel) and production years. The statistically treatment of the results allowed us to assess the chemotype, the quality of Reggio Emilia watermelon and to obtain analytical traceability of the product.


2014 - Application of 2D NMR spectroscopy to Lambrusco Wine [Abstract in Atti di Convegno]
Graziosi, Riccardo; Bertelli, Davide; Papotti, Giulia; Plessi, Maria
abstract

In recent times the interest in analytical methods, able to assess the origin and authenticity of foodstuff from raw materials to final commercial products, has grown considerably. The complex composition of the samples represents the main difficulty in the characterization of food products. Foods usually occurs as a complex mixture of many chemically different components often present in different ratios. This fact make difficult to use non separative techniques. To solve this problem many analytical approaches have to be taken into account, and the full characterization often requires information gathered through different analytical methods. Non separative analytical techniques can be particularly useful for the characterization of food and for solving traceabilyty problems. Among these techniques, Nuclear Magnetic Resonance spectroscopy has drawn particular attention. Many works based on NMR coupled with multivariate data analysis have been conducted, concerning the usability and effectiveness of this technique as a fingerprint analysis tool in food chemistry, and in particular in oenology.1,2 The main strengths of NMR are its short sample preparation and the wide range of chemical compounds that can be detected simultaneously. NMR, can rapidly provide spectra that describe the main molecular profile with high reproducibility, without laborious sample pre-treatments. For this purpose, one-dimensional sequences are normally used. The two-dimensional sequences, though requiring more time, are very rich in information. However, the spectra obtained by 2D NMR are difficult to use for statistical purposes, due to their intrinsic complexity and the very high number of variables to consider . The aim of this research is to demonstrate that it is possible to use a 2D sequence for the study and classification of typical PDO Lambrusco wines of Modena. The study of new analytical approaches able to characterize and assess the authenticity of typical oenological products is certainly an element that strengthens the bond with the territory of origin and promotes the consumer’s perception of greater quality.


2014 - HPLC-Ms characterization of phenylpropanoid glycosides from Aloysia polystachya (Griseb. et Moldenke) [Abstract in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Graziosi, Riccardo; Plessi, Maria
abstract

Aloysia polystachya (Griseb. et Moldenke) is a herbaceous aromatic plant of the Verbenaceae family, widely distributed in subtropical regions of South America, mainly Paraguay and the north of Argentina, commonly known as “burrito” or “té-burro” (Botta, 1979). The leaves are prepared as an aqueous infusion or decoction, commonly used as dietary supplement or a tea substitute in daily life, as a remedy to treat all kind of gastrointestinal disorders, such as spasm or indigestion, pain, nausea, vomiting, dyspepsia and gastritis (Martìnez Crovetto, 1981; Martìnez & Pochettino, 1992; Filipov, 1994; Alonso & Desmarchelier, 2005). The leaves of Aloysia spp., among phenolic compounds, such as flavonoids, and phenolic acids, contain also phenylpropanoid glycosides, water-soluble compounds widely distributed, most of them deriving from medicinal herbs. Among them, verbascoside is the most abundant one in Aloysia spp.. To our knowledge, data on the chemical characterization of Aloysia polystachya (Griseb. et Moldenke) are poor in the literature, and, in particular, no study on the phenylpropanoid glycosides has been performed to date. In this work, HPLC-MS qualitative determination of the phenylpropanoid glycosides fraction, purified by Solid Phase Extraction (SPE), in Aloysia polystachya (Griseb. et Moldenke) extract was performed. Two different MS techniques have been coupled to HPLC: ion trap tandem-mass spectrometry (IT-MS), and the quadrupole-time of flight-mass spectrometry (Q-TOF-MS). The LC-IT-MS analyses were employed to support tentative structure identification, on the basis of m/z values of detected ions. The LC-Q-TOF-MS analysis enabled to calculate the accurate mass measurements, provided the most probable molecular formula, and is useful to identify the compounds present in the extract. Nine phenylpropanoid glycosides were identified in methanolic extract of the Aloysia polystachya (Griseb. et Moldenke) leaves. Among them, the compounds forsythoside A, plantainoside C, purpureaside D, martynoside and its two isomers were identified here for the first time. The results present here could be helpful in the future developing and validating of an analytical method to quantify the isolated compounds, and to assess the quality of Aloysia polystachya (Griseb. et Moldenke) leaves. Knowledge of the content of phenylpropanoid glycosides could further contribute to the chemotaxonomy of the genus.


2014 - HPLC_MS characterization of the antocyanin fraction of italian sweet cherry (prunus avium L.) [Abstract in Atti di Convegno]
Bertelli, Davide; Graziosi, Riccardo; Papotti, Giulia; Plessi, Maria
abstract

Sweet cherries (Prunus avium L.) are very attractive fruits for their taste and color attributes, as well as for their abundance of nutrients. Emilia Romagna Region, in conjunction with Puglia, Campania and Veneto, is one of the most typical production areas, and the harvests from Vignola area, where many sweet cherry cultivars are grown, are well known and appreciated. Cherry is rich in phenolic compounds (Usenik et al. 2008), principally known for its antioxidant properties, particularly useful against free radicals and diseases derived from them. The main phenolic antioxidants found in cherries are anthocyanins. Anthocyanins, responsible for the color of the fruit and the pulp (Mylnikov et al. 2005), represent a wide class of molecules, belonging to the family of flavonoids, phenolic substances widely distributed in the plant kingdom. This class of molecules is well known for their health-promoting effects, in particular for their free radical scavenging ability, which helps preventing cancer, cardiovascular diseases and retarding the aging process. In the present study, we characterized the anthocyanin fraction of 9 sweet cherry cultivars, grown in an experimental field of Vignola (Emilia Romagna). To achieve our purpose, it was developed an extraction and purification method by SPE. The anthocyanin fraction extracted was then characterized by HPLC-MS. The identification was carried out by analysing the MS and MS2 fragmentation pattern and by comparing our results with literature data. Eight molecules have been identified in all. The Moretta is distinguished from other cultivars for the high anthocyanin content. This study aims to enhance the cherry fruit quality, focusing on healthy compoundss, especially considering the recent achievement of the PGI (Protected Geographical Indication) designation of origin in 2012.


2014 - In vivo penetration of bare and lipid-coated silica nanoparticles across the human stratum corneum [Articolo su rivista]
Iannuccelli, Valentina; Bertelli, Davide; Romagnoli, Marcello; S., Scalia; Maretti, Eleonora; Sacchetti, Francesca; Leo, Eliana Grazia
abstract

Skin penetration of silica nanoparticles (NP) currently used in pharmaceutical and cosmetic products is a topic of interest not only to evaluate their possible toxicity, but also to understand their behaviour upon contact with the skin and to exploit their potential positive effects in drug or cosmetic delivery field. Therefore, the present work aimed to elucidate the in vivo mechanism by which amorphous hydrophilic silica NP enter human stratum corneum (SC) through the evaluation of the role played by the nanoparticle surface polarity and the human hair follicle density. Two silica samples, bare hydrophilic silica (B-silica, 162 ± 51 nm in size) and hydrophobic lipid-coated silica (LC-silica, 363 ± 74 nm in size) were applied on both the volar and dorsal side of volunteer forearms. Twelve repetitive stripped tapes were removed from the human skin and evaluated for elemental composition by Energy Dispersive X-ray (EDX) analysis and for silicon content by Inductively Coupled Plasma quadrupole Mass Spectrometry (ICP-MS). All the stripped tapes revealed nanosized structures generally located in the broad spaces between corneocytes and characterized by the same elemental composition (relative weight percentage of silicon and silicon to oxygen weight ratio) than that of the applied samples. However, only about 10% B-silica permeated until the deepest SC layers considered in the study indicating a silica retention in the upper layers of SC, regardless of the hair follicle density. Otherwise, the exposure to LC-silica led to a greater silica skin penetration extent into the deeper SC layers (about 42% and 18% silica following volar and dorsal forearm application, respectively) indicating that the NP surface polarity played a predominant role on that of their size in determining the route and the extent of penetration.


2014 - Italian propolis composition in term of geographical origin [Abstract in Atti di Convegno]
Bertelli, Davide; Graziosi, Riccardo; Papotti, Giulia; Plessi, Maria; Marcazzan, Gian Luigi; Gardini, Silvia
abstract

Italian’s Propolis is a product rich in flavonoid aglycones (flavones and flavanones), phenolic acids and esters of phenolic acids. This composition is characteristic for propolis produced in Europe. However, Italy is marked by three prevailing climatic zones : Mountain, Continental and Maritime which select areas with different flora and consequent botanical plant sources. Poplar’s buds are known to be the main source of propolis for honey bees, but poplar trees do not grow at high altitude where there are mainly deciduous beech forests or coniferous forests and on the other hand along the coast the vegetation is compoused by Mediterranean scrub and shrubs. The purpose of this study was to evaluate the different composition of propolis from different Italian areas and observe the profile of phenolic acids and flavonoids. Several samples of propolis were collected along Italian's country, including islands, in 2013. It was not been requested to beekeepers a specific way of picking up but only they had to ensure that the hives were of permanent stations in order to correlate closely the samples to the territory of origin. Ethanol extracts of propolis (EPP) was obteined by soxtleth method according to in accordance to argentina regulation IRAM - INTA 15935-1. Samples were previously defined in their resinous percentage composition in relation to the wax and mechanical impurities. The resinous fraction was then analyzed and evaluated. The molecules were chosen in accordance with the data reported in literature, being these the most representative for the European propolis. About twenty molecules of phenolic acids and flavonoids were quantified with the external standard method. Separation and quantification of the compounds was performed by a chromatography with mass spectrometer detector (HPLC-Q/MS-MS ). The analysis on the samples was performed also by spectrophotometric techniques. (Finally, the bioactive properties of resinous extract were Studied also in terms of reducing power and radical scavenging effect). The data were then processed by statistic analysis to identify groups and connections with the geographical and climatic zone of origin.


2014 - NUTRASCIENCE s.r.l. [Spin Off]
Bertelli, Davide; Plessi, Maria; Pellati, Federica; Forni, Flavio; Papotti, Giulia; Graziosi, Riccardo
abstract


2014 - 2D NMR spectroscopy in food science: an innovative approach to spectra processing and statistical data analysis [Abstract in Atti di Convegno]
Graziosi, Riccardo; Bertelli, Davide; Papotti, Giulia; Annalisa, Maietti; Paola, Tedeschi; Plessi, Maria
abstract

NMR spectroscopy is nowadays applied to a wide range of matrices, regardless of their physical state, with some relevant advantages: samples remain unchanged, it is possible to obtain information regarding different class of molecules with one acquisition and the production of dangerous waste is avoided. The use of 1H NMR in foods is of particular interest, especially when coupled with chemometrics and multivariate statistical analysis, techniques that have been applied to quality control studies and in the assessment of botanical and geographical origin of foods. This kind of procedure has been applied to many products, from oils to honey (Bertelli et al. 2010), from beverages like beer, tea and coffee to oenological products like wine and vinegar (Bertelli et al 2012). Nevertheless, the majority of those applications regards monodimensional NMR, since this kind of spectra is usually faster to acquire and easier to use, while 2D spectra often require more complex procedures. To overcome this limitation, we are developing a tool for the analysis of bidimensional spectra, able to import and analyse them using Matlab environment. This software is able to use instrumental data as raw signals, by unfolding each spectra into a vector, as well as a whole image, using a pattern recognition procedure. To evaluate the applicability and the effectiveness of this approach, a set of PDO Lambrusco wines and of Balsamic and Traditional Balsamic Vinegar of Modena have been analysed, acquiring 1H-13C HMBC spectra using a 400 NMR spectrometer. The obtained spectra were first processed by means of the developed software, then generated datasets have been analysed using multivariate statistical methods. Results shows that the tool, even if still under development, is able to exploit 2D NMR spectra, making possible to build classificatory models using extracted informations.


2013 - An efficient chemical analysis of phenolic acids and flavonoids in raw propolis by microwave-assisted extraction combined with high-performance liquidchromatography using the fused-core technology [Articolo su rivista]
Pellati, Federica; Prencipe, FRANCESCO PIO; Bertelli, Davide; Benvenuti, Stefania
abstract

A closed-vessel microwave-assisted extraction (MAE) technique was optimized for the first time for the extraction of polyphenols from raw propolis. The results obtained by means of response surface experimental design methodology showed that the best global response was reached when the extraction temperature was set at 106°C, the solvent composition close to EtOH-H2O 80:20 (v/v), with an extraction time of 15min. In comparison with other techniques, such as maceration, heat reflux extraction (HRE) and ultrasound-assisted extraction (UAE), the extraction with MAE was improved by shorter extraction time and lower volume of solvent needed.The HPLC analyses of propolis extracts were carried out on a fused-core Ascentis Express C18 column (150 mm×3.0 mm I.D., 2.7 μm), with a gradient mobile phase composed by 0.1% formic acid in water and acetonitrile. Detection was performed by DAD and MS.The method validation indicated that the correlation coefficients were >0.999; the limit of detection was in the range 0.5-0.8. μg/ml for phenolic acids and 1.2-3.0. μg/ml for flavonoids; the recovery range was 95.3-98.1% for phenolic acids and 94.1-101.3% for flavonoids; the intra- and inter-day %RSD values for retention times and peak areas were ≤0.3 and 2.2%, respectively.The quali- and quantitative analysis of polyphenols in Italian samples of raw propolis was performed with the validated method. Total phenolic acids ranged from 5.0 to 120.8. mg/g and total flavonoids from 2.5 to 168.0. mg/g.The proposed MAE procedure and HPLC method can be considered reliable and useful tools for the comprehensive multi-component analysis of polyphenols in propolis extracts to be used in apitherapy.


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 - Capitolo 11: Aceto [Capitolo/Saggio]
Plessi, Maria; Bertelli, Davide
abstract

Vengono elencate e descritte le principali analisi previste dalle normative vigenti sugli aceti.


2013 - Characterization and classification of propolis extracts by HR-NMR [Abstract in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Graziosi, Riccardo; Plessi, Maria
abstract

Propolis is a resinous substance collected by bees from exudates of different plants, rich in health-relevant phenolic compounds [1]. This study demonstrates that it is possible to use HR-NMR for the simultaneous recognition of 12 typical phenolic compounds (apigenin, chrysin, galangin, kaempferol, quercetin, naringenin, pinocembrin, pinostrobin, caffeic acid, cinnamic acid, p-coumaric acid and ferulic acid) [2] in propolis extracts, using appropriate tools for spectra pre-treatment [3] and analysis, and to verify if the same technique was able to classify propolis according to the harvesting method. A simple 1H-NMR sequence was used for phenolic compounds identification. Sixty-five propolis samples were used to test the proposed identification procedure. Ten out of 12 considered compounds were identified as statistically significant in most of the samples. For the propolis classification according to the harvesting method, the ethanolic extracts were initially analysed for quantification of the main bioactive substances, balsams and waxes. The 1H-NMR and heteronuclear multiple bond correlation spectra were then acquired and analysed by multivariate statistical techniques. The best model was obtained using the 1H-NMR by analysing the spectral region between 4.50 and 13.00 ppm (predictive capacity: 96.7%).


2013 - Characterization of Protected Designation of Origin Lambrusco wines of Modena using NMR spectroscopy and multivariate statistical analysis [Abstract in Atti di Convegno]
Graziosi, Riccardo; Papotti, Giulia; Bertelli, Davide; Plessi, Maria
abstract

Lambrusco are a Protected Designation of Origin (PDO) red wines produced in the province of Modena, one of the most relevant wine-producing region in Italy. For these wines also exists a production code, establishing the ampelographic composition depending on their geographical and historical region of origin. The application of NMR to food as quality control is a subject of great interest and represents an important tool to counter adulteration and sophistication [1]. In the present work we have employed NMR spectroscopy as a molecular fingerprint technique and control tool, allowing us to evaluate the authenticity of analysed wines. Using 1H NMR, 1H-13C HMBC, 1H-13C HSQC analyses as well as literature data, it has been possible to identify several metabolites. We have also applied several pattern recognition procedures, both unsupervised and supervised, to data sets obtained from 1H NMR, to achieve a reliable classification of the different wine samples. PCA was performed to verify the intrinsic variation in the data sets, while PLS-DA was applied to maximize separation between samples. In conclusion, it has been possible to successfully classify the samples depending on their varietal origin using 1H NMR coupled with chemometrics, and to identify the most relevant compounds, responsible for the varietal discrimination.


2013 - Comparative Evaluation of the Effect of Permeation Enhancers, Lipid Nanoparticles and Colloidal Silica on in vivo Human Skin Penetration of Quercetin [Articolo su rivista]
Scalia, S; Franceschinis, E; Bertelli, Davide; Iannuccelli, Valentina
abstract

The aim of this study was to evaluate emulsions containing a penetration enhancer, lipid nanoparticles (LNs) or colloidal silica as systems to improve the topical delivery of the flavonoid quercetin. Methods: The skin penetration of quercetin was investigated in vivo on human volunteers by tape stripping. Quercetin-loaded LNs were prepared using hot high-pressure homogenization and characterized by means of dynamic light scattering and release studies. The location of the silica nanoparticles in the skin was determined by inductively coupled plasma mass spectrometry assay of silicon in the stratum corneum strips. Results and Conclusions: The penetration enhancer diethylene glycol monoethyl ether did not produce any significant increase in the fraction of the applied quercetin dose permeated in vivo into human stratum corneum (17.1 ± 3.2%) compared to the control emulsion (18.1 ± 2.3%). A greater but statistically nonsignificant accumulation of the flavonoid in the human horny layer (21.2 ± 2.9% of the applied dose) was measured following topical application of quercetin-loaded LNs (mean particle size: 527 nm). On the other hand, the addition of colloidal silica (average particle diameter: 486 nm) to the emulsion (2%, w/w) significantly increased the in vivo uptake of quercetin by the human stratum corneum to 26.7 ± 4.1% of the applied dose, the enhancing effect on permeation being more marked in the deepest horny layer strips. The measured in vivo skin penetration profile of colloidal silica showed that silica particles diffused down to the intermediate region of the human horny layer and hence could act as carrier for quercetin.


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 - Gas chromatography combined with mass spectrometry, flame ionization detection and elemental analyzer/isotope ratio mass spectrometry for characterizing and detecting the authenticity of commercial essential oils of Rosa damascena Mill. [Articolo su rivista]
Pellati, Federica; Orlandini, Giulia; K. A., van Leeuwen; G., Anesin; Bertelli, Davide; M., Paolini; Benvenuti, Stefania; F., Camin
abstract

RATIONALE The essential oil of Rosa damascena Mill. is known for its fine perfumery application, use in cosmetic preparations and for several pharmacological activities. Due to its high value, it can be easily adulterated with flavors or cheaper oils. This study is aimed at a detailed phytochemical characterization of commercial samples of R. damascena essential oil and at their authenticity assessment. METHODS Nineteen commercial samples of R. damascena essential oil of different geographic origin and an additional authentic one, directly extracted by hydro-distillation from fresh flowers, were considered. GC-MS and GC-FID techniques were applied for the phytochemical analysis of the samples. EA-IRMS (Elemental Analysis–Isotope Ratio Mass Spectrometry) and GC/C(Combustion)-IRMS were used to determine the delta-13C composition of bulk samples and of some specific components. RESULTS Citronellol (28.7-55.3%), geraniol (13.5-27.3%) and nonadecane (2.6-18.9%) were the main constituents of Bulgarian and Turkish essential oils, while those from Iran were characterized by a high level of aliphatic hydrocarbons (nonadecane: 3.7-23.2%). The delta-13C values of bulk samples were between –28.1 and –26.9‰, typical for C3 plants. The delta-13C values of specific components were in the usual range for natural aromatic substances from C3 plants, except for geranyl acetate, which displayed higher values (up to –18‰). These unusual delta-13C values were justified by the addition of a natural cheaper oil from a C4 plant (Cymbopogon martinii, palmarosa), which was found to occur in most of the essential oils. CONCLUSION GC/C-IRMS, in combination with GC-MS and GC-FID, can be considered as an effective and reliable tool for the authenticity control of R. damascena essential oil.


2013 - In vivo silica nanoparticle translocation across human stratum corneum: the effect of surface hydrophobization in relation to hair follicle density. [Abstract in Atti di Convegno]
Iannuccelli, Valentina; Bertelli, Davide; Romagnoli, Marcello; Maretti, Eleonora; Sacchetti, Francesca; Leo, Eliana Grazia
abstract

Insoluble nano- and submicron-scale metal dioxides are widely used in pharmaceutical and cosmetic formulations designed for being applied on the skin surface and acting mainly as thickeners, sunscreens and pigments. Since it’s primarily for the insoluble nanoparticles that health concerns related to possible skin uptake arise, the EU requires producers to submit a detailed safety report on the nanomaterials used as well as declaring their presence on the label. As noted in the 2007 FDA Nanotechnology Task Force report, there may be a higher degree of uncertainty associated with nanoscale materials compared to conventional chemicals, both with respect to knowledge about them and the way that testing is performed. Indeed, the issue of insoluble nanoparticle skin penetration, mainly focusing on nanosized TiO2 and ZnO, is still controversial, divided between a penetration limited to the hair follicles and the translocation across the lipid pathway within SC cells sometimes reaching living skin cells. Among the metal dioxide materials, colloidal silicon dioxide, a submicroscopic amorphous hydrophilic silica is one of the most used in terms of commercial production amounts together with TiO2, ZnO and silver nanoparticles. With regard to topical formulations, it is used to stabilize emulsions and as a thixotropic thickening or suspending agent in gels, microemulsions, and semisolid preparations. Although amorphous silica is generally regarded as an essentially nontoxic and non-irritant excipient [1] also proposed for implants, the nano-scale feature might alter the bioavailability of the cosmetic formulation [2]. Actually, silica nanoparticles have been shown in vitro to modulate the diffusion through animal skin of hydrophilic and hydrophobic model drugs (caffeine, retinol, quercetin) from topical emulsions to affect skin properties and also to penetrate up to the viable epidermis and upper dermis of excised porcine skin [3, 4]. Previously, we demonstrated on human beings that colloidal silica is able to penetrate in the upper region of the human stratum corneum (SC) and different mechanisms of translocation were hypothesized [4]. A similar finding arose from a research on ultra-fine TiO2 [5]. Therefore, the goal of the present work was to investigate in vivo the mechanism of silica entry into SC by means of qualitative and quantitative assays performed on stripped tapes removed from volunteers treated with silica incorporated in a standard cream. With this objective, the study took into account the influence of human hair follicle density by means of sample application on both volar and dorsal forearm. Moreover, by considering that skin surface is hydrophobic and skin penetration requires particle wetting by the SC lipids, the effect of silica surface hydrophobization was also investigated. Twelve repetitive tape strips removed from each forearm of the volunteers following sample application were evaluated by EDX analysis by points. All the tapes removed from the skin that has received silica and H-silica application showed nanosized and nearly spherical structures generally located in rather broad intercellular spaces. Their EDX spectra exhibited the characteristic peaks owing to X-ray emission from Si atoms (Fig. n. 1). The relative weight percentages of the metal and the metal to oxygen weight ratio were found to be equivalent to those detected in the samples before their application. These findings could give evidence of a movement of both the nanoparticles across the outermost part of SC reaching the corneum compactum along broad channels between the corneocytes. Silicon quantitative analysis carried out on the removed tapes indicated silica accumulation in the outer part of SC corresponding to the corneum disjunctum and its significant decrease inside the deepest tapes, regardless of the sample and the hair follicle density. Nevertheless, the higher silica level detect


2013 - Phenolics characterization in propolis using HR-NMR and chemometrics [Abstract in Atti di Convegno]
Bertelli, Davide; Papotti, Giulia; Graziosi, Riccardo; Plessi, Maria
abstract

Propolis is a resinous substance produced by bees collecting resinous substances from exudates of different plants now widely used in the preparation of supplements and nutraceuticals, which is rich in well-known health-relevant phenolic compounds such as flavonoids and phenolic acids. Propolis extracts are very complex matrices difficult to study. Different analytical methods are usable to analyse propolis extracts and to obtain chemical fingerprint but at our knowledge NMR was not previously used for this purpose. This study aims to demonstrate that it is possible to use the 1H NMR for the simultaneous identification of phenolic compounds in propolis extracts, using appropriate tools for spectra pre-treatment and analysis. In this work as first step, twelve typical phenolic propolis compounds (apigenin, chrysin, galangin, kaempferol, quercetin, naringenin, pinocembrin, pinostrobin, caffeic acid, cinnamic acid, p-coumaric acid, ferulic acid) were considered as reference compounds and their presence in samples were verified by HPLC-MS, then NMR coupled with chemometric techniques were applied on the same samples. A simple 1H NMR sequence was used to obtain spectra of samples. Spectra were pre-treated by using an appropriate tool for spectra alignment and analysed by using a software for the study of spectra originated from complex matrices aiming to the recognition of the selected substances from their principal NMR signals. Sixty-five propolis samples were used to test the proposed identification procedure. Ten out of twelve considered compounds were identified as statistically significant in most of the samples. This work suggests that it is possible to efficiently use the 1H NMR, coupled with appropriate spectral analytical tools, for the simultaneous detection of phenolic compounds in complex matrices.


2013 - Phytochemical analysis and authenticity control of commercial essential oils and absolutes of Rosa damascena Mill. [Abstract in Atti di Convegno]
F., Camin; K. A., van Leeuwen; Orlandini, Giulia; M., Paolini; Bertelli, Davide; Pellati, Federica
abstract

The essential oil of Rosa damascena Mill. is known for its fine perfumery application, use in cosmetic preparations and for several pharmacological activities. Due to its high value, it can be easily adulterated with flavors or cheaper oils. In this study we considered 24 commercial samples of R. damascena essential oil and absolute of different geographic origin. GC-MS and GC-FID techniques were applied for the phytochemical analysis of the samples. EA-IRMS (Elemental Analyser–Isotope Ratio Mass Spectrometry) and GC/C(Combustion)-IRMS were used to determine the δ13C composition of bulk samples and of some specific components. Citronellol (28.7-55.3%), geraniol (13.5- 27.3%) and nonadecane (2.6-18.9%) were the main constituents of Bulgarian and Turkish essential oils. The samples from Iran were characterized by a high level of aliphatic hydrocarbons (nonadecane: 3.7-23.2%), while in the Turkish absolute rose and in the oils from Morocco and Ukraine phenylethyl alcohol was the main constituent (47.6-75.4%). The δ13C values of bulk samples were in the range between –29 and –26.9‰, typical for C3 plants. For most of the analyzed compounds in the essential oils and absolutes, the δ13C values were in the usual range for natural aromatic substances from C3 plants, except for geranyl acetate, which displayed higher values (up to –18‰). These unusual δ13C values could be justified by the addition of a natural cheaper oil from a C4 plant (Cymbopogon martinii, palmarosa). A synthetic origin was moreover postulated for geranyl acetate in the absolute from Ukraine. The results indicated that GC/C-IRMS, in combination with GC-MS and GC-FID, represents an effective and reliable tool for the authenticity control of R. damascena essential oil.


2013 - Skin penetration of colloidal silica [Abstract in Atti di Convegno]
S., Scalia; V., Trotta; Bertelli, Davide; Iannuccelli, Valentina
abstract

Colloidal silica is widely used in topical products for its effect on the rheology of the formulations. It is considered a non-toxic and non-irritant excipient and it is included in the European and US Pharmacopoeias. However, in vitro investigations have shown a pro-inflammatory stimulation of endothelial cells induced by exposure to silica particles of nano-size. In the light of the recent concern about the potential toxicological risk associated with topically applied nanoparticles, aim of the present study was to investigate the in vivo skin penetration profile of commercial colloidal silica from a model cream (oil-in-water emulsion) preparation. Colloidal silica (Aerosil 200; BET specific surface area, 200 m2/g) was incorporated in the water phase of the test emulsion, after dispersion by sonication (15 min). The emulsion was applied at a level of 4 mg/cm2 to the forearm of the volunteers, in accordance with the local Ethics Committee requirements and the percutaneous permeation of the silica nanoparticles was assessed by the tape-stripping technique. The tapes were collected separately and the silica distribution in each group of tapes was determined by inductively coupled plasma quadrupole mass spectrometry assay of the silicon content of the strips. Total recovery of colloidal silica (sum of silicon unabsorbed and transferred to the strips) was 97.8%. Negligible amounts (1.5 μg/cm2 ± 0.2) of silicon were detected in the tapes from the stratum corneum exposed to the control formulation without silica. On the other hand, the majority (58.9%) of the applied silica nanoparticles was found to diffuse up to the intermediate region of the human horny layer, with only 2.1% detected in the deepest strip. Since the silica particles used in the present investigation were mainly confined to the upper stratum corneum layers, potential toxicological risk should be limited.


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 - Chemical and Functional Characterization of Italian Propolis Obtained by Different Harvesting Methods [Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; L., Bortolotti; Plessi, Maria
abstract

The composition and the antioxidant activity of Italian poplar propolis obtained using three harvesting methods and extracted with different solvents were evaluated. Waxes, balsams, resins contents were determined. Flavones and flavonols, flavanones and dihydroflavonols and total phenolics were also analyzed. To characterize the phenolic composition, the presence of 15 compounds was verified through HPLC-MS/MS. The antioxidant activity was evaluated through 1,1-diphenyl-2-picrylhydrazyl radical and reducing power assays. The ability of propolis to inhibit the lipids oxidation was monitored by analyzing the hydroperoxides and TBARS formation in lipids incorporated into an O/W emulsion. Acetone shows the highest extraction capacity. The wedges propolis have the highest concentration of active phenolic compounds (TP = 359.1 ± 16.3 GAEs/g; TFF = 5.83 ± 0.42%; TFD = 7.34 ± 1.8%) and seem to be the most promising for obtaining high-value propolis more suitable to prepare high quality dietary supplements. (TBARS = 0.012 ± 0.009 mmol std/g; RP = 0.77 ± 0.07 TEs/g).


2012 - Development of an extraction and purification method for the characterization of the high molecular weight fraction of traditional balsamic vinegar [Abstract in Rivista]
Graziosi, Riccardo; Bertelli, Davide; Papotti, Giulia; Plessi, Maria
abstract

Traditional balsamic vinegar (TBV) is a seasoning produced in the provinces of Modena and Reggio Emilia (Italy) and known and appreciated worldwide. During his years-long seasoning many chemical reactions takes place, leading to the formation of antioxidants and bioactive compounds, including melanoidins [1]. They are a class of polymeric substances originating from sugars and amino acids, as a consequence of Maillard’s reaction. In literature only a relatively low number of studies on melanoidins contained in foods are present, mainly because of objective difficulties in their isolation. For this reason we decided to develop a method suitable for the extraction and the purification of high molecular weight melanoidins from a complex matrix, such as vinegars. Extraction with solvents as reported by Xu et.al [2], dialysis and ultrafiltration, were tested on TBV and on a good quality industrial balsamic vinegar (IBV). On the obtained fractions dry matter, antioxidant power and total phenolic content were determined. To evaluate the effect of purification procedures, 1H-NMR spectra of the different fractions were also recorded and compared to raw vinegars spectra. In the ultrafiltered sample low molecular weight compounds were still presents, so it is possible to affirm that dialysis is crucial to obtain an effective purification of the melanoidins. Nevertheless it is noticeable that polyphenols concentration is higher in ultrafiltered samples: although this step is not suitable, alone, to achieve a satisfactory purification, it is useful to concentrate the high molecular weight fraction isolated by dialysis in a smaller volume. IBV showed a behavior very similar to TBV, but its high molecular weight fraction generally presents a lower phenols concentration and antioxidant activity. Moreover, in general, does not appear to exist any kind of correlation between the fractions molecular weight and their antioxidant capacity. In conclusion, the combination between dialysis and ultrafiltration appears to be a valid procedure to extract and purify the high molecular weight fraction of TBV in a small volume, but results obtained from dialysis alone are more consistent and reproducible.


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 - 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 - Protein extraction and identification as a honey adulteration detection method. [Abstract in Rivista]
Bertelli, Davide; Graziosi, Riccardo; Papotti, Giulia; Plessi, Maria
abstract

Honey is a nutritious and healthy natural food produced by honey bees from plant nectars: it consists mostly of the sugars glucose and fructose, as well as maltose, sucrose, water, pollen and other minor components. Food authentication is an international issue in quality control and food safety. Regulatory authorities, food processors, retailers, and consumers are interested in knowing the origin and quality of foods; for these reasons the deliberate mislabeling and adulteration of foods, particularly honeys, are matters of increasing global concern. Many studies have reported on the chemical constituents of honey such as sugars and flavonoids, and the analysis of many of those components is applicable to adulteration detection. Another approach is based on analysis of proteins, the honey contains many different proteins in minute quantities and several enzymes, such as amylase, α-glucosidase, β-glucosidase and glucose oxidase. Since they originate from Apis mellifera, the identification of a protein or an enzyme of a different origin could be interpreted as a proof of adulteration. We have focused on the detection of an α-amylase from Aspergillus niger, an enzyme that can be employed to produce glucose syrup, used for honey adulteration. This enzyme was added to honey samples in different concentration, ranging from 0,1 to 1 nmol/ml, and different isolation and analysis techniques were tested. Honey samples were dialyzed against ultrapure water for 3 days using a cellulose membrane with a 12KDa cutoff, then lyophilized to concentrate the residue protein. Passivation of the membrane to avoid loss of protein during the dialysis was also tested, but no significative difference was found after determination with Bradford assay. A separation using disposable C18 SPE column was also tested. Samples obtained after isolation were analyzed using both MALDI-TOF MS and HPLC CHIP Q-TOF MS. The sensitivity of MALDI-TOF resulted much lower than the one achieved with HPLC-MS, which was able to detect concentration as low as 0,1 nmol/ml for dialyzed samples. The separation obtained with the SPE columns was not satisfactory, probably because amylase was strongly bound to the C18 column and elution was not efficient.


2012 - USe of HR-NMR for functional properties estimation of balsamic vinegar of Modena [Abstract in Rivista]
Bertelli, Davide; A., Maietti; Papotti, Giulia; P., Tedeschi; Graziosi, Riccardo; G., Bonetti; V., Brandolini; Plessi, Maria
abstract

Over the past few years, many works based on proton NMR coupled with multivariate data analysis were been conducted concerning the study of the suitability of HR-NMR as fingerprint analysis tool in the study of vinegars. Classical studies on vinegars 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 chemometrics certainly is a useful tool in this regard. In this context, the aim of the present work was to select and optimize a NMR sequences to characterize the Balsamic vinegar of Modena and the Traditional Balsamic vinegar of Modena and to study the possibility to obtain by NMR spectra useful informations about the biologically active compounds and the functional properties. 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. The NMR spectra will be correlated with some analytical parameters such as total polyphenols, total condensed tannins, total flavonoid and total antioxidant activity determined by several methods (ABTS, DPPH, photochemiluminescence). The different methods selected for the determination of the antioxidant activity allow the assessment of different aspects of the oxidation process: the DPPH and ABTS assays are based on both HAT (hydrogen-atom abstraction) and SET (electron transfer reaction) mechanisms; the photochemiluminescence (PCL) method is based on the photo induced autoxidation inhibition of luminol by antioxidants mediated from the radical superoxide. In this way, the measured antioxidant activity can be compared to antioxidant activity of the balsamic vinegar in biological systems.


2012 - Use of HS-SPME-GC-MS for the classification of Italian lemon, orange and citrus spp. honeys [Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; Plessi, Maria
abstract

Volatile compounds from 90 Italian citrus honeys of different varieties (lemon, Citrus limon (L.)30 Burm., orange, Citrus sinensis (L.) Osbeck, and citrus, Citrus spp.), 30 provided by CRA-API31 (Consiglio per la Ricerca e la Sperimentazione in Agricoltura-Unità di ricerca di apicoltura e32 bachicoltura) (Bologna, Italy) and 60 purchased on the local markets, were analysed in order to33 classify them according to the characteristic aroma profiles. The HS-SPME-GC method previously34 developed and validated in our laboratory was applied. Factor Analysis and General Discriminant35 Analysis were carried out on peaks and intensity data for the honey samples classification.36 Statistical analyses revealed a good separation between honey samples, the best model indeed37 shows a 66.5% of total variance explained by the first canonical function (CF1) and a predictive38 capacity of 78.9%. The most significant compounds responsible for the observed separation were39 assigned to lilacaldehyde isomers, 1-p-menthen-9-al isomers, dill ether, limonene, limonen-10-ol40 and undecanal.


2012 - Utilizzo di Hr-NMR per la caratterizzazione di vini Lambrusco DOP di Modena [Abstract in Atti di Convegno]
Graziosi, Riccardo; Bertelli, Davide; Papotti, Giulia; Plessi, Maria
abstract

Negli ultimi anni, diversi autori hanno dimostrato la validità dell’uso della tecnica NMR per la tracciabilità varietale e geografica e la sua efficacia nello studio di prodotti enologici, in particolare del vino [1, 2].In questo lavoro l’HR-NMR è stata utilizzata come impronta digitale di alcuni vini Lambrusco DOP di Modena (Lambrusco di Sorbara, Lambrusco Salamino di Santa Croce and Lambrusco Grasparossa di Castelvetro) allo scopo di servire come indicatore indiretto di autenticità e controllo di qualità. Elaborare nuovi approcci analitici in grado di caratterizzare e accertare l’autenticità di vini Lambrusco DOP è sicuramente un elemento che rafforza il legame con il territorio d'origine e che promuove la percezione del consumatore di una maggiore tutela e qualità di questi prodotti.I dati ottenuti sono stati elaborati con tecniche chemiometriche multivariate in grado di interpretare efficacemente gli spettri derivanti dalle analisi mono e bi dimensionali (HR-1H-NMR, 1H-1H COSY, 1H-13C HMBC).


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 - 1H NMR simultaneous identification of health-relevant compounds in propolis extracts [Articolo su rivista]
Bertelli, Davide; Papotti, Giulia; L., Bortolotti; G. L., Marcazzan; Plessi, Maria
abstract

AbstractIntroduction- Propolis is a resinous substance collected by bees from exudates of different plantswhich is rich in well-known health-relevant phenolic compounds such as flavonoids and phenolicacids. Propolis extracts are very complex matrices difficult to study. Different analytical methodsare usable to analyse propolis extracts and to obtain chemical fingerprint but at our knowledgeNMR was not previously used for this purpose.Objective- This study aims to demonstrate that it is possible to use the 1H NMR for thesimultaneous recognition of phenolic compounds in complex matrices, such as propolis extracts,using appropriate tools for spectra pre-treatment and analysis.Methodology- In this work twelve typical phenolic propolis compounds (apigenin, chrysin,galangin, kaempferol, quercetin, naringenin, pinocembrin, pinostrobin, caffeic acid, cinnamic acid,p-coumaric acid, ferulic acid) were considered as reference compounds and their presence insamples were verified by HPLC-MS. A simple 1H NMR sequence was used to obtain spectra ofsamples. Spectra were pre-treated by using an appropriate tool for spectra alignment and analysedby using a software for the study of spectra originated from complex matrices. Sixty-five propolissamples were used to test the proposed identification procedure.Results- Ten out of twelve considered compounds were identified as statistically significant in mostof the samples.Conclusion- This work suggests that it is possible to efficiently use the 1H NMR, coupled withappropriate spectral analytical tools, for the simultaneous detection of phenolic compounds incomplex matrices.


2011 - Analisi di estratti di propoli mediante HR-NMR e software per analisi di miscele complesse. [Relazione in Atti di Convegno]
Bertelli, Davide; Papotti, Giulia; Plessi, Maria
abstract

Viene descritto l'utilizzo dell'NMR per lo studio delle componenti bioattive di estratti di propoli mediante l'utilizzo di software per il pretrattamento, l'elaborazione e l'analisi di spettri monodimensionali.


2011 - Caratteristiche chimico-fisiche e nutrizionali di cultivar di ciliegio nel vignolese [Abstract in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Graziosi, Riccardo; Papotti, Giulia; S., Zocca
abstract

Le ciliegie (Prunus Avium L.) sono frutti apprezzati dai consumatori per la precocità e le eccellenti qualità nutrizionali ed organolettiche. In questo lavoro sono state studiate le sostanze fenoliche e l’attività antiossidante di campioni provenienti da coltivazioni biologiche e convenzionali, raccolti nel corso di cinque successive stagioni produttive. I risultati sono concordi con la letteratura esistente e l’alta variabilità dimostra il peso dell’andamento stagionale sulle qualità dei frutti. I risultati confermano l’ottima qualità funzionale delle ciliegie, in particolare della cultivar Moretta, che si propone come un ottimo prodotto per il mantenimento del buono stato di salute dei consumatori.


2011 - Caratterizzazione nutrizionale e funzionale di cultivar di ciliegia [Capitolo/Saggio]
Bertelli, Davide; Papotti, Giulia; Cancellieri, Giuseppina; Plessi, Maria; S., Zocca
abstract

Lavoro pubblicato nel volume stampato in occasione del VII Festa Nazionale dell'Associazione Nazionale citta delle Ciliegie


2011 - Caratterizzazione di lambruschi doc dell'emilia tramite hr-nmr ed analisi statistica multivariata [Abstract in Atti di Convegno]
Graziosi, Riccardo; Bertelli, Davide; Papotti, Giulia; Plessi, Maria
abstract

I vini noti come Lambruschi sono originari del territorio emiliano, dove vengono coltivati da secoli e sono quindi profondamente radicati nella tradizione contadina locale. La zona di produzione tradizionale è rappresentata dalle provincie di Modena e Reggio Emilia, dove esistono specifici disciplinari di produzione per i Lambruschi D.O.C. Lo scopo della presente ricerca è stato quello di valutare l’efficacia della spettroscopia HR-NMR nel fornire informazioni di fingerprint molecolare, tali da poter essere utilizzate a scopo chemiometrico e classificatorio. A questo scopo sono state applicate tecniche di analisi statistica multivariata agli spettri mono e bidimensionali, ottenuti dopo l’ottimizzazione delle sequenze NMR. Data la complessità della matrice alimentare in esame è infatti stato necessario individuare, selezionare ed ottimizzare le sequenze più efficienti nell’estrarre informazioni rilevanti dai campioni. Informazioni che hanno reso possibile la costruzione di modelli chemiometrici, in grado di discriminare tra loro le diverse tipologie di Lambrusco. Questo studio ha quindi permesso di individuare ed ottimizzare le metodiche analitiche e le sequenze NMR necessarie e di valutare le tecniche chemiometriche più efficaci da applicare al tipo di spettri che si ottengono dal vino. Il metodo analitico impiegato è quindi stato sfruttato per affrontare un problema relativamente semplice, come la classificazione varietale dei Lambruschi, con l’obiettivo finale di applicarlo in un prossimo futuro alla risoluzione di problemi legati all’origine geografica dei prodotti.


2011 - Chromatographic Methods for Metabolite Profiling of Virus- and Phytoplasma-Infected Plants of Echinacea purpurea [Articolo su rivista]
Pellati, Federica; F., Epifano; N., Contaldo; Orlandini, Giulia; L., Cavicchi; S., Genovese; Bertelli, Davide; Benvenuti, Stefania; M., Curini; A., Bertaccini; M. G., Bellardi
abstract

This study was focused on the effects of virus and phytoplasma infections on the production of Echinacea purpurea(L.) Moench secondary metabolites, such as caffeic acid derivatives, alkamides, and essential oil. The identification of caffeic acid derivatives and alkamides was carried out by means of high-performance liquid chromatography-diode array detection (HPLC-DAD), HPLC-electrospray ionization-mass spectrometry (ESI-MS), and MS2. Quantitative analysis of these compounds wascarried out using HPLC-DAD. The results indicated that the presence of the two pathogens significantly decreases (P < 0.05) the content of cichoric acid, the main caffeic acid derivative. Regarding the main alkamide, dodeca-2E,4E,8Z,10E/Z-tetraenoic acid isobutylamide, a significant decrease (P < 0.05) in the content of this secondary metabolite was observed in virus-infected plants in comparison with healthy plants, while in the phytoplasma-infected sample the variation of this secondary metabolite was not appreciable. The % relative area of the E/Z isomers of this alkamide was also found to change in infected samples. The gas chromatography (GC) and GC-MS analysis of E. purpurea essential oil enabled the identification of 30 compounds. The main significant differences (P < 0.05) in the semiquantitative composition were observed for three components: limonene, cis-verbenol, and verbenone. The results indicate that the presence of virus and phytoplasma has an appreciable influence on the content of E. purpurea secondary metabolites, which is an important issue in defining the commercial quality, market value, and therapeuticefficacy of this herbal drug.


2011 - Classificazione di Propoli in base al metodo di raccolta mediante l'analisi di fingerprint NMR [Relazione in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Plessi, Maria; G. L., Marcazzan
abstract

Odore, colore, aspetto e composizione chimica della propoli variano non solo in base alle diverse fonti botaniche da cui deriva, all'origine geografica ed alle condizioni climatiche [Bankova et al., 2002], ma anche in base al metodo di produzione [Rossi, 2006]. Considerato il crescente interesse per questo prodotto, il presente studio è stato condotto per valutare se l'HR-NMR, utilizzata come tecnica di analisi del fingerprint chimico, accoppiata a metodi statistici multivariati sia in grado di classificare la propoli di pioppo a seconda del metodo di produzione e di fornire conoscenze supplementari. Per ridurre l’influenza sulla composizione dovuta all’origine geografica, alla fonte botanica ed alla stagionalità, tutti i campioni di propoli sono stati forniti direttamente da alcuni apicoltori locali e dal CRA-API e sono stati raccolti da colonie situate in una ristretta area geografica dell’Emilia Romagna, in cui la specie Populus è quella dominante ed è noto che le api producono propoli soprattutto dagli essudati di pioppo. Sessanta propoli raccolte con diversi metodi (17 per raschiamento, 26 tramite spessori di legno, 17 da reti di plastica) sono state oggetto dello studio. Prima di eseguire gli esperimenti NMR, l’origine di pioppo [Popova et al, 2007] è stata confermata tramite la quantificazione delle sostanze bioattive (polifenoli totali, flavoni e flavonoli totali, flavanoni e diidroflavonoli totali) e di balsami, che in questo tipo propoli sono presenti in rapporti caratteristici. Su tutti i campioni a disposizione sono state eseguite le analisi 1H-NMR e bidimensionale eterocorrelata Heteronuclear Multiple Bond Correlation (HMBC). Il modello migliore (79.4% di varianza complessiva spiegata dalla prima funzione discriminante, 96.7% di capacità predittiva) si ottiene utilizzando la risonanza magnetica nucleare del protone con il vantaggio che questa è la tecnica più semplice e che richiede i minori tempi di acquisizione. L'uso della tecnica HR-NMR, accoppiata a metodi statistici multivariati, sembra quindi essere in grado di sviluppare dei modelli sufficientemente efficaci per la classificazione della propoli secondo i metodi di produzione e quindi si può proporre come efficace metodo per il controllo di qualità della propoli.


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 - Impiego di HR-NMR per la caratterizzazione di lambruschi DOC dell'Emilia [Relazione in Atti di Convegno]
Bertelli, Davide; Papotti, Giulia; Graziosi, Riccardo; Baschieri, Carlo; Plessi, Maria
abstract

I vini conosciuti come Lambruschi provengono da un gruppo di vitigni presenti da secoli nel territorio dell' Emilia e profondamente radicati nella tradizione contadina locale. Storicamente, le zone di produzione si trovano nelle province di Modena e Reggio Emilia. La produzione e la commercializzazione di tutti questi vini D.O.C. è regolamentata da specifici disciplinari di produzione. Lo scopo della presente ricerca è stato quello di mettere a punto un metodo per l’analisi e la caratterizzazione di vini Lambruschi DOC dell’Emilia utilizzando la Risonanza Magnetica Nucleare ad alta risoluzione (HR-NMR) mono e bidimensionale. Gli spettri ottenuti dopo ottimizzazione delle sequenze di acquisizione NMR sono stati poi impiegati per la costruzione di modelli chemiometrici mediante tecniche statistiche multivariate, in grado di discriminare tra loro le diverse tipologie di Lambrusco. Questo lavoro va considerato come studio pilota volto allo scopo di valutare l’efficacia della HR-NMR nel fornire informazioni di fingerprint molecolare dei prodotti considerati di qualità tale da poter essere utilizzate a scopo chemiometrico e classificatorio. Per fare tutto ciò si è dovuto innanzitutto individuare, selezionare e ottimizzare le sequenze migliori nell’estrarre informazioni dai campioni queste sequenze sono quindi state sfruttate per affrontare un problema relativamente semplice come la classificazione varietale dei Lambruschi, con l’obiettivo finale di applicarle in un prossimo futuro alla risoluzione di problemi legati all’origine geografica dei prodotti. Tutto questo ha permesso di individuare ed ottimizzare le metodiche analitiche e le sequenze NMR necessarie e di valutare le tecniche chemiometriche più opportune ed efficaci da applicare al tipo di spettri che si ottengono dal vino. I risultati migliori sono stati ottenuti utilizzando 1H-NMR accoppiata con analisi statistiche supervisionate come l’analisi discriminante (GDA). L’approccio seguito ha fornito buoni risultati, sia in termini di qualità del segnale NMR ottenuto che delle tecniche chemiometriche applicate, e permette di affermare che le metodiche approntate sono in grado di estrarre informazioni di qualità dagli spettri registrati tali da essere con ogni probabilità sfruttabili anche per procedere ad una futura costruzione di modelli atti alla discriminazione geografica dei prodotti enologici.


2011 - Microparticulate polyelectrolyte complexes for gentamicin transport across intestinal epithelial [Articolo su rivista]
Iannuccelli, Valentina; Montanari, Monica; Bertelli, Davide; Pellati, Federica; Coppi, Gilberto
abstract

Polysaccharide microparticles for the oral administration of gentamicin were designed in order to obtainan increased drug absorption by means of microparticle transport across the intestinal epithelia. Alginate/chitosan microparticles with a size of ∼ 2 μm were developed by spray-drying a water solution containingthe drug complexed with the polyanionic alginate and subsequent alginate cross-linking process bycalcium ions and chitosan. The pre-formulation study, performed by changing the concentration of bothcross-linkers, led to the selection of the most suitable formulation which was assayed for its capacity to be translocated across intestinal epithelia, via both M cells contained in Follicle Associated Epithelium (FAE) ofPeyer’s patches and enterocytes of the mucosal epithelium. An ex vivo perfusion technique of rabbit andrat intestinal tissues containing Peyer’s patches combined with an in vitro method by using Caco-2 cellmonolayers demonstrated the microparticulate carrier ability to be taken up by both M cells and enterocytes.However, only the endocytosis by M cells appeared to provide the microparticle transport from theepithelium toward deeper sub-epithelial regions.


2011 - Qualità chimica e funzionale di propoli italiana ottenuta con diverse tecniche di produzione [Relazione in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; L., Bortolotti; Plessi, Maria
abstract

Il principale problema relativo al controllo di qualità ed alla standardizzazione della propoli è l’elevata variabilità di composizione che dipende dalla fonte botanica, dal clima, dall’origine geografica. Il profilo chimico della propoli Italiana è tipicamente quello della propoli proveniente da pioppo che in Italia rappresenta la principale fonte botanica di approvvigionamento per le api. Nel 2007 Popova et al. suggerirono le seguenti caratteristiche tipiche per la propoli di pioppo, sfruttabili per la standardizzazione ed il controllo di qualità: balsami, minimo 45%; polifenoli totali, minimo 21%; flavoni e flavonoli totali, minimo 4%; flavanoni e dihydroflavonoli, minimo 4%. La propoli può poi essere caratterizzata dal contenuto in flavonoidi e in fenoli, aventi un ruolo cruciale come marcatori tassonomici. In questo contesto, è stato eseguito uno studio di controllo di qualità di propoli italiane di pioppo al fine di verificare l’effetto sulla qualità chimica e funzionale dei più comuni metodi di produzione. Sono stati quindi analizzati 20 campioni di propoli forniti direttamente dal CRA-API prodotti da colonie situate nel campo sperimentale dello stesso istituto, al fine di ridurre al minimo l’influenza sulla composizione dovuta all’origine geografica, alla stagionalità e alla fonte botanica. I 20 campioni sono stati ottenuti con le seguenti tecniche di produzione: 6 per raschiamento, 8 tramite spessori di legno, 6 da reti di plastica. Su questi campioni sono stati valutati i contenuti di cere, resine, balsami e delle principali classi di composti bioattivi (fenoli totali, flavoni, flavonoli, flavanoni e diidroflavonoli) e l’attività antiossidante di estratti in quanto tali ed incorporati in un sistema emulsionato.I contenuti di cere, balsami e resine sono per gran parte in accordo con i dati della letteratura, in cui è riportato che la propoli ottenuta da spessori mostra il più basso contenuto di cere ed il più elevato contenuto di resine [Rossi, 2006]. Il contenuto di balsami rappresenta una caratteristica importante di qualità, dal momento che sono questi a contenere i composti bioattivi. I risultati relativi alla composizione in principi attivi e alla attività antiossidante mostrano che il sistema di produzione possiede una qualche influenza sulla qualità della propoli.


2011 - THE QUALITY OF HONEY FOR BEES AND MAN [Capitolo/Saggio]
L., Bortolotti; P., Truchado; A., Allende; Kaatz, H. H.; Bertelli, Davide; Plessi, Maria; K., Bíliková; J., Šimúth; R. F. A., Moritz; F. A., Tomás Barberán; Ag, Sabatini
abstract

Honey is used both as food ingredient and in a variety of treatments for diverse ailments. For this reason, consumer expectation of its quality and purity is particularly high. The aim of the BEE SHOP Honey Department was the evaluation of honey quality and authenticity, through the development of new instrument for the verification of the botanical origin and the presence of impurities. Honey quality can be important also for the colony itself and therefore the Honey Department focused on the physiological properties of honey which can be beneficial for honeybees and for the prevention of bee diseases. Testing the origin of honeybees is also important to enforce the EC directive for organic beekeeping, since the use of regional bee strains is an important quality criterion for organic honey. To identify the origin of the honeybee the BEE SHOP Honey Department has developed a DNA based diagnostic tool. Through the analysis of honey and nectar samples by HPLC-MS-MS methods, suitable markers were detected for Robinia, Tilia, Citrus, Eucalyptus and chestnut unifloral honeys, and the following phytochemicals have been proposed for the determination of honey floral origins: myricetin, tricetin and luteolin for Eucalyptushoney, kynurenic acid related compounds for chestnut honey, terpenoids for Linden honey, hesperetin for Citrus honey, kaempferol rhamnosides for Acacia (Robinia) honey. Two novel protocols were introduced for the evaluation of honey quality: DRIFTS (Diffuse Reflectance Infrared Fourier Transform Spectroscopy) and HR-NMR (High Resolution Nuclear Magnetic Resonance). These techniques, coupled with appropriate multivariate statistical analysis, demonstrated to be suitable for the verification of botanical origin and the detection of honey adulteration by sugar syrups. The HR-NMR method seems to be suitable also for a quantitative determination of the adulteration levels. A new sensitive enzyme-linked immunoassay (ELISA) for the quantitative determination of apalbumin1a major compound of the royal jelly (RJ) proteins in honey has been developed. This protein can be used as a marker for honey quality because its concentration varies with the botanical origin. The highest content was determined in chestnut honey, in comparison with acacia and rape honey, while the lowest amount was detected in honey obtained supplying bee colony with saccharose syrup. The antimicrobial potential of honey based on proteins of honeybee origin was tested by microtiter based assays. The inhibition of P. larvae growth was observed in the protein fraction of cherry and rape honeys and honeydew. Moreover, a protein fraction corresponding to apalbumin2a has been identified in honey. This protein, purified from RJ, had specific antibiotic properties against P. larvae. The anti quorum-sensing (QS) activities of honeys with different floral origin have been evaluated, using bacterial strains in which quorum-sensing activated the pigment violacein. 29 honey samples inhibited QS even at the lowest concentration. The anti-QS activity was concentration-dependent and relied on the floral origin. Among all honeys, chestnut and linden samples were the strongest quorum-sensing inhibitors (QSI).


2011 - Valore funzionale di ciliegie da varie cultivar [Abstract in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Graziosi, Riccardo; Papotti, Giulia; S., Zocca
abstract

Sweet cherries (Prunus Avium L.) are highly appreciated fruits for their excellent nutritional and functional values, and the “Ciliegia di Vignola” trademark is well known in region Emilia Romagna as well as in Italy. Between the various cultivars grown in the area, traditional ones such as Anellone, Nero I, Nero II and Moretta are the most important. The chemo-physical characterization of sweet cherries and the research of component of particular interest has been carried out by others authors in the recent past. For these reason we have decided to study some functional properties of sweet cherries coming from the Vignola area. Samples belonging to nine different cultivars, grown in an experimental camp, were harvested during years 2006-2010 at commercial ripening. For each cultivar samples grown with both organic (O) and conventional (C) farming were harvested. Total phenolic substance, total anthocyanins, Fe2+ chelating activity, antioxidant and reducing power were determined in each sample. The extracts were obtained using acidified methanol from 20g of exactly weighted of edible matter. Total phenolic determination has been carried out using the Folin-Ciocalteu method and expressed as mg of gallic acid per 100g of edible matter. Total anthocyanins determination has been carried out using the colorimetric pH differential method, measuring the absorbance at 510 nm at pH 1 and 4.5. The difference between measured absorbance is proportional to the anthocyanins content, expressed as mg of cyanidine per 100g of edible matter. Antioxidant power has been evaluated measuring the inhibition of a constant quantity of a stable radical (DPPH, 2,2-diphenyl-1-picrylhydrazyl), expressed as trolox µeq per g. Reducing power and Fe2+ chelating activity are two useful properties for the evaluation of antioxidant properties: the former has been measured using Oyaizu method, while the latter has been evaluated using Dinis method. For these determination, measured absorbance of a standardized volume of sample has been used as an activity index. Results obtained with these analysis are generally in agreement with those reported in literature. In some cases standard deviation is considerably high: this is due to the difference in the climatic condition during the ripening process in the considered years. There are no significant differences between samples grown with conventional and organic farming, thus confirming that the organic approach can produce fruits with the same functional properties than the conventional one. The most interesting cultivar, because of its high phenolic contents and superior antioxidant activity, is certainly Moretta. The cultivar Nero II also shows interesting functional properties, while cultivar Sweetheart is characterized by the lowest measured values. Reported results confirm the good functional properties of sweet cherries in general and of Moretta cultivar in particular. It is therefore possible to say that the consumption of those fruits in a balanced diet can have a positive effect on the health of the consumer.


2010 - Detection of Honey Adulteration by Sugar Syrups Using One-dimensional and two-dimensional High-resolution Nuclear Magnetic Resonance [Articolo su rivista]
Bertelli, Davide; Lolli, Massimo; Papotti, Giulia; L., Bortolotti; G., Serra; Plessi, Maria
abstract

The importance of honey adulteration detection has recently increased owing to the limited production levels in recent years and to the relative high price of honey, therefore this illegal practice has becoming more and more attractive to producers. Hence the need has arisen for more effective analitical methods aiming at detecting honey adulteration. The present research presents an effective method to detect adulteration in honey falsified by intentional addition of different concentrations of commercial sugar syrups, using one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) coupled with multivariate statistical analysis. Sixty-three authentic and 63 adulterated honey samples were analysed. To prepare adulterated honeys, 7 different sugar syrups normally used for nutrition of bees were used. The best discriminant model was obtained by 1D spectra and the leave-one out cross-validation showed a predictive capacity of 95.2 %. Also 2D NMR have furnished acceptable results (cross-validation correct classification 90.5%), although the 1H-NMR sequence is preferable because it is the simplest and fastest NMR technique.


2010 - Use of HR-NMR to classify propolis obtained using different harvesting methods [Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; Plessi, Maria; Rossi, Maria Cecilia
abstract

Propolis has various biological activities closely related to the composition which varies according to environmental factors and also to the method of production. The present study was aimed at determining whether or not HR-NMR and multivariate statistical analysis were able to classify propolis according to the method used to harvest it. Sixty propolis samples were analysed in all. The ethanolic propolis extracts were initially analysed for quantification of the main bioactive substances, balsams and waxes. The 1H NMR and heteronuclear multiple bond correlation (HMBC) spectra were then acquired. Spectral data were analysed by application of multivariate statistical techniques (Factor Analysis and General Discriminant Analysis). The best results were obtained using the 1H NMR which furnishes a sufficiently effective model by analysing the spectral region between 4.50 and 13.00 ppm (predictive capacity: 96.7%).Keywoards: propolis; NMR; chemometrics; harvesting methods; chemical fingerprint.


2010 - Valutazione dell'autenticità del miele mediante HR-NMR [Abstract in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Cancellieri, Giuseppina; L., Bortolotti; Plessi, Maria
abstract

Il miele è uno dei più complessi alimenti prodotti dalla natura e un dolcificante che può essere utilizzato dall’uomo senza alcuna lavorazione.L’adulterazione del miele è un fenomeno tornato ad essere economicamente rilevante dopo le ultime annate di produzione che sono risultate particolarmente scarse a causa dei ben noti problemi di spopolamento degli alveari. Per il controllo della qualità dei mieli, atto a scoprire adulterazioni, sono stati proposti ed utilizzati diversi metodi analitici basati su tecniche HPLC, GC-MS, IC[1]. Recentemente sono state proposte anche tecniche spettroscopiche come medio-infrarosso (MIR) e spettroscopia Raman. Scopo del presente lavoro è l’applicazione della la 1H-NMR per la ricerca dell’adulterazione del miele effettuata con sciroppi zuccherini normalmente utilizzati per la nutrizione invernale delle api. L’applicazione della HR-NMR all’analisi del miele è di recente sviluppo ed in generale a nostra conoscenza, non è mai stata precedentemente utilizzata a questo scopo [2-4]. Sono stati analizzati 63 campioni di mieli di acacia autentici, forniti da apicoltori dell’Emilia Romagna e dal CRA-API, e 63 campioni degli stessi mieli adulterati dal 10 al 40% con 7 sciroppi zuccherini commerciali. Gli spettri ottenuti sono stati utilizzati come fingerprint dei campioni ed analizzati mediante tecniche statistiche multivariate e i modelli ottenuti sono risultati efficaci nell’individuare i campioni adulterati, in particolare, l’analisi discriminante generale ha permesso di ottenere in fase di validazione crociata una capacità predittiva superiore al 95%.


2009 - Classification of Italian propolis by HR-NMR: influence of different production techniques [Abstract in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Plessi, Maria
abstract

Propolis, a complex resinous substance collected by bees, has been known for its healing properties. It has various biological activities related to the chemical composition which varies according to its variety, the geographical source and also the method of harvest. The influence of the method of production on the composition and the properties of propolis seems to be related with the recognized behavior of the bees that cover the smooth and narrow surfaces, as the thin space created by the wedges, with propolis that is purer and richer in balsams, whereas they use the propolis mixed with major amount of waxes to cover the irregular surfaces of the beehive or the plastic nets used for the propolis production. Considering the widespread use of propolis products and the increased interest concerning the characterization of chemical composition, the present study was conducted to evaluate if the HR-NMR used as chemical fingerprint analysis coupled with multivariate statistical methods is able to classify poplar propolis according to the method of harvest and to gain extra knowledge concerning the fingerprint of propolis. In this regard, 60 raw propolis collected with different methods by several local beekeepers and by CRA-API (Consiglio per la Ricerca e la Sperimentazione in Agricoltura-Istituto Nazionale di Apicoltura e Bachicoltura) (Bologna, Italy) were extracted with ethanol and, before performing the NMR experiments, were analyzed for quantification of the main bioactive substances of poplar type propolis (total phenolics, total flavones and flavonols, total flavanones and dihydroflavonols) and balsams, to confirm the poplar source. The ethanolic propolis extracts were analyzed by HR-NMR using both 1H NMR and HMBC. Spectral data were analyzed by application of multivariate statistical techniques (FA and GDA). The best results were obtained using the 1H NMR which enabled to develope a sufficiently effective and appropriate model.


2009 - Methyl anthranilate content in Italian citrus honey determined by HS-SPME-GC [Articolo su rivista]
Papotti, Giulia; Bertelli, Davide; M., Lolli; A. G., Sabatini; Plessi, Maria
abstract

An headspace solid phase microextraction-gas chromatography (HS-SPME-GC) method, previously developed and validated, was applied to the determination of the methyl anthranilate (MA) content of 75 Italian citrus honeys (11 of lemon, 44 of orange and 20 of Citrus spp.). Twenty-four samples were purchased on the local market and 51 were provided by CRA-API (Consiglio Nazionale per la Ricerca e Sperimentazione in Agricoltura-Istituto Nazionale di Apicoltura e Bachicoltura) (Bologna, Italy). All the samples had a MA content above the limit of detection (LOD) (0.149 μg g−1) of the analytical method. The concentration range was between 0.46 and 2.52 μg g−1 and the overall average MA content was 1.19 μg g−1. The honeys with the highest mean MA content were the orange honeys followed by Citrus spp. and lemon (1.29 ± 0.461, 1.12 ± 0.511 and 0.92 ± 0.39 μg g−1, respectively). No significant differences were measured between commercial and authenticated samples.


2008 - Analisi ATR-FTIR per la valutazione dello stato ossidativo di grassi animali [Relazione in Atti di Convegno]
Bertelli, Davide; Plessi, Maria; Lolli, Massimo; Papotti, Giulia
abstract

L’Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) ha trovato recenti applicazioni anche in campo alimentare per la determinazione di zuccheri, alcaloidi, acidi grassi, ecc. I principali vantaggi di questa tecnica sono quello di non richiedere alcun tipo di preparazione del campione e la elevatissima velocità di esecuzione che la rendono adatta anche ad applicazioni in linea di produzione. Lo scopo di questo lavoro è quello di studiare la possibilità di utilizzare la ATR per studiare lo stato ossidativo di grassi di origine animale.


2008 - Antioxidant activity of propolis in oil-in-water emulsion [Abstract in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide
abstract

In this work, it has been developed an appropriate soybean oil-in-water emulsion system to study the antioxidant activity of different type of propolis extracts. Emulsions were stored at room temperature and under magnetic stirring for the entire period of analysis (10 days). Lipid hydroperoxides were measured according to the method described by Shantha and Decker.1 The secondary oxidation products were determined as TBARS according to the method described by McDonald and Hultin.2 The surface of the emulsion droplets was varied by using different surfactants, sodium dodecyl sulphate (SDS) is an anionic emulsifier, whereas Tween 80 and Brij 35 are non ionic surfactants. The Tween 80-stabilized emulsion oxidation rate is lower than Brij 35 and SDS emulsions. Besides, the Tween 80 emulsion resulted to be more stable then the others and it was used to determine the effects of pH on lipid oxidation. The lipid oxidation rate of the Tween 80-stabilized emulsion was tested at pH 3.0 and 7.0. Oxidation rate increases with decreasing pH and the oxidation rate at pH 3.0 is more desirable since the oxidation rate at pH 7.0 is too much low. As a consequence, the Tween 80-stabilized emulsion at pH 3.0 has been chosen for our purpose. For each propolis extract (ethanolic, acetonic, chloroformic, etheric), 3 oil-in-water emulsions were prepared by adding 0.06 ml, 0.27 ml and 1 ml of extract into the oil phase. All the extracts show antioxidant activity which, in all cases except for the acetonic one, tends to increase with increasing the extract content. Instead, the ethanolic extract used at low level presents an evident pro-oxidant effect. The lowest content of acetonic extract is the most active as antioxidant.


2008 - Attività antiossidante di propoli in emulsioni O/A [Relazione in Atti di Convegno]
Papotti, Giulia; Plessi, Maria; Bertelli, Davide; M., Rancan; A. G., Sabatini
abstract

Per valutare correttamente il fenomeno ossidativo e il potenziale antiossidante della propoli è necessario sviluppare modelli che ne riproducano le condizioni chimiche, fisiche ed ambientali. A questo scopo si prestano bene sistemi modello in emulsione. In questo lavoro, è stato sviluppato un sistema di emulsioni O/A per lo studio dell’attività antiossidante di differenti estratti di propoli incorporati nella fase lipidica.


2008 - Caratterizzazione funzionale di cultivar di ciliegia. [Relazione in Atti di Convegno]
Plessi, Maria; Lolli, Massimo; Bertelli, Davide; Papotti, Giulia; S., Zocca
abstract

Le ciliegie (Prunus Avium L.) sono frutti apprezzati dai consumatori per la loro precocità e le eccellenti qualità nutrizionali ed organolettiche. In Emilia Romagna ed anche a livello nazionale ed internazionale è da tempo apprezzato il marchio “Ciliegia di Vignola”, che è attribuito alle ciliegie coltivate nel comune di Vignola e nelle zone limitrofe. Tra le cultivar presenti in zona di particolare importanza sono le tradizionali, Anella, Nero I, Nero II, Moretta, Della Marca. La nostra regione è all’avanguardia nella coltivazione biologica: conta più di 4000 operatori ed oltre l’8% della superficie coltivata. La caratterizzazione chimico fisica e la ricerca di particolari componenti delle ciliegie sono state oggetto di studio anche nel recente passato. Per queste ragioni abbiamo ritenuto interessante studiare alcuni parametri nutrizionali e funzionali di ciliegie provenienti da coltivazioni biologiche e convenzionali della zona di produzione tipica.


2008 - Classification of Italian Honeys by 2D HR-NMR [Articolo su rivista]
Lolli, Massimo; Bertelli, Davide; Plessi, Maria; A. G., Sabatini; Restani, Cinzia
abstract

The importance of honey has been recently increased because of its nutrient and therapeutic effects, but the adulteration of honey in terms of botanical origin has increased, too. The floral origin of honeys is usually determined using melisso-palynological analysis and organoleptic characteristics, but the application of these techniques requires some expertise. A number of papers have confirmed the possibility of characterizing honey samples by selected chemical parameters. In this study high-resolution nuclear magnetic resonance (HR-NMR) and multivariate statistical analysis methods were used to identify and classify honeys of five different floral sources. The 71 honey samples (robinia, chestnut, citrus, eucalyptus, polyfloral) were analyzed by HR-NMR using both 1H NMR and heteronuclear multiple bond correlation spectroscopy (HMBC). Spectral data were analyzed by application of unsupervised and supervised pattern recognition and multivariate statistical techniques such as principal component analysis (PCA) and general discriminant analysis (GDA). The use of 1H−13C HMBC coupled with appropriate statistical analysis seems to be an efficient technique for the classification of honeys.


2008 - Determinazione di metile antranilato in mieli di agrumi italiani mediante HS-SPME-GC [Relazione in Atti di Convegno]
Papotti, Giulia; Bertelli, Davide; Lolli, Massimo; Plessi, Maria; A. G., Sabatini
abstract

In Italia, il miele di agrumi più comunemente prodotto è quello di arancio o di agrumi misti: più rari i mieli di un’unica varietà diversa dall’arancio (limone, bergamotto, cedro, mandarino). Il profilo aromatico è uno dei fattori più tipici dei prodotti alimentari, sia per le proprietà organolettiche, che determinano la qualità dell’alimento, sia per l’autenticità del prodotto stesso. Il metile antranilato, in particolare, è stato proposto come un indicatore di qualità del miele di agrumi nel 1988 da Serra Bonvehì. Lo sviluppo di metodi analitici per la determinazione del contenuto di MA nel miele di agrumi è un argomento di grande interesse per l’uso che certi paesi fanno di questo analita come marker d’origine botanica per questo tipo di miele, nonostante, al momento non esistano metodiche ufficialmente riconosciute per questa determinazione. Per queste ragioni, nel nostro laboratorio, è stato sviluppato, ottimizzato e validato mediante experimental design un metodo basato sulla tecnica HS-SPME-GC.


2008 - Development of an HS-SPME-GC method to determine the methylanthranilate in Citrus honeys. [Articolo su rivista]
Bertelli, Davide; Papotti, Giulia; Lolli, Massimo; A. G., Sabatini; Plessi, Maria
abstract

An efficient and simple method for determination of methyl anthranilate (MA) in Citrus spp. honeys by headspace-solid-phase microextraction-gas chromatography (HS-SPME-GC) was developed and validated. Experimental design was used to investigate the effects of the principal extraction parameters. The central composite design (CCD) and the desirability function were used to find the experimental conditions providing the optimal HS-SPME result. Validation was carried out in terms of specificity, linearity, limit of detection (LOD) and quantitation (LOQ) (0.149 and 0.324 μg/g, respectively), method precision (RSD 7%), LOQ precision (RSD 6.5%), and was resulted accurate and robust. Finally, the applicability of the method to the determination of MA in a number of commercial Citrus spp. honey samples was demonstrated, the content ranged from 0.63 to 3.26 μg/g.


2008 - Development of new methods for the evaluation of honeyquality and authenticity. [Abstract in Atti di Convegno]
Lolli, Massimo; Bertelli, Davide; Plessi, Maria; L., Bortolotti; M., Rancan; A. G., Sabatini
abstract

The evaluation of honey quality and authenticity is one of the main target in beekeeping research. It involves the evaluation of authenticity in respect of description (botanical and geographical origin) and in respect of production (presence of defects or adulterations).Within the Beeshop research project, three different analytical methods were developed and tested for the determination of honey quality: DRIFTS (Diffuse Reflectance Infrared Fourier Transform Spectroscopy), 1D and 2D HR-NMR spectroscopy (High Resolution Nuclear Magnetic Resonance), All the methods were applied to the evaluation of botanical origin of the honey samples collected by Beeshop members, and to the analysis of honey samples artificially adulterated by sugar syrups. The results of DRIFTS and 2D HR-NMR methods, analysed with general discriminant analysis (GDA), show a classification capability for the botanical origin of 92,56% and 97% respectively. The two methods, coupled with appropriate multivariate statistical analysis, seem to be efficient and versatile techniques for the classification of the botanical origin, and are able to detect honey adulteration by sugar syrup.By means of 1D HR-NMR spectroscopy good results were achieved for the adulteration level in honey samples. Also DRIFTS and 2D HR-NMR spectroscopy appears to be suitable for the determination of honey adulteration by sugar syrup, but it will be necessary to greatly increase the number of acquisitions and replicates.


2008 - Physicochemical characteristics and antioxidant activity of sweet cherry for organic and conventional farming system. [Relazione in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Lolli, Massimo; Papotti, Giulia; S., Zocca
abstract

Anthocyanin, total phenolic content, antioxidant activity, reducing power, chelating activity and some otherbphysicochemical parameters were measured in organic and conventional samples of six cultivars of sweet cherry (prunus avium).


2008 - Quantificazione di glucosio e fruttosio nel miele mediante HR-NMR [Relazione in Atti di Convegno]
Lolli, Massimo; Papotti, Giulia; Bertelli, Davide; F., Grillenzoni; Plessi, Maria; A. G., Sabatini
abstract

Gli zuccheri rappresentano più del 95% della sostanza secca del miele ed il loro elevato contenuto contribuisce in modo determinante a definirne numerose proprietà fisiche e nutrizionali: la viscosità, l’igroscopicità, lo stato fisico (liquido o cristallizzato), il valore energetico, il potere dolcificante. I due zuccheri principali sono il glucosio e il fruttosio, che insieme costituiscono circa il 90% del totale. Il rapporto tra i due zuccheri è variabile ed il contenuto di fruttosio è di solito leggermente superiore, solo in alcuni tipi di miele primaverili, come quelli di tarassaco e di colza, avviene il contrario. Il rapporto tra fruttosio e glucosio è molto importante, infatti un elevato contenuto di glucosio, relativamente poco solubile in acqua, determina una maggiore tendenza alla cristallizzazione. Oltre alla classica gascromatografia ed alla HPLC, le tecniche più utilizzate in passato per la determinazione di glucosio e fruttosio nel miele sono state metodiche IR. In questo lavoro abbiamo voluto verificare la possibilità di utilizzare due tecniche 2D HR-NMR per la simultanea valutazione del contenuto dei due zuccheri.


2008 - Use of HR-NMR for the study of honey adulteration [Abstract in Atti di Convegno]
Lolli, Massimo; Plessi, Maria; Bertelli, Davide; Papotti, Giulia; A. G., Sabatini
abstract

The importance of honey adulteration detection has recently increased owing to the limited production levels in recent years and to the relative high price of honey, therefore this illegal practice has becoming more and more attractive to producers. The present research presents an effective method to detect adulteration in honey falsified by intentional addition of different concentrations of commercial sugar syrups, using one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) coupled with multivariate statistical analysis.The best discriminant model was obtained by 1D spectra.


2008 - Uso della spettrometria HR-NMR per lo studio dell'adulterazione del miele [Relazione in Atti di Convegno]
Lolli, Massimo; Plessi, Maria; Bertelli, Davide; M., Rancan; A. G., Sabatini
abstract

L’aggiunta al miele di sciroppi zuccherini, utilizzati per la nutrizione delle api e per trattamenti veterinari, comunemente ottenuti dall’idrolisi dell’amido o dall’inversione del saccarosio, è uno dei possibili metodi di adulterazione in apicoltura, e rappresenta un complesso problema, che può avere indiscutibili conseguenze nutrizionali ed organolettiche. In passato sono stati utilizzati molti metodi di controllo per accertare l’autenticità del miele: HPLC, GC-MS, IC, MIR. L’utilizzo della spettrometria di risonanza magnetica nucleare ad alta risoluzione per evidenziare questo problema è invece più recente ed, in particolare, la 2D NMR non è mai stata applicata precedentemente.


2007 - Classification of Italian honeys by mid-infrared diffuse reflectance spectroscopy (DRIFTS) [Articolo su rivista]
Bertelli, Davide; Plessi, Maria; A. G., Sabatini; Lolli, Massimo; F., Grillenzoni
abstract

Diffuse reflectance mid-infrared Fourier transform spectroscopy (DRIFTS) and multivariate statistical analysis methods were used for the identification and classification of honey from different floral sources. The 82 honey samples (robinia, chestnut, citrus, polyfloral) were scanned by DRIFTS in the region 4000–600 cm−1 and also transformed in 1st and 2nd derivatives. Spectral data were analyzed by principal component analysis, general discriminant analysis and classification tree analysis. Classification accuracy near 100% was obtained by discriminant and classification tree analyses. Classification models were successfully validated with one-third leave out method and a classification of about 100% were achieved.


2007 - Determination of methyl anthranilate byHS-SPME-GC in italian citrus honey [Abstract in Atti di Convegno]
Papotti, Giulia; Plessi, Maria; Bertelli, Davide; Lolli, Massimo; A. G., Sabatini
abstract

An headspace solid phase microextraction-gas chromatography (HS-SPME-GC) method, previously developed and validated in our laboratory through the central composite design (CCD) and the desirability function methods to find the experimental conditions providing the optimal HS-SPME result, was applied to the determination of the methyl anthranilate (MA) content in a number of Italian Citrus spp. honey samples,


2007 - Distribution of metals and phenolic compounds as a criterion to evaluate variety of berries and related jams [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Albasini, Albano
abstract

Polyphenols, anthocyanins, phosphate, iron, zinc, manganese, calcium, potassium, magnesium and sodium were evaluated both in berries belonging to the genera Rubus and Ribes and in related jams by means of spectrophotometric techniques, to verify a possible differentiation on the basis of these parameters. The phenolic and anthocyanins higher contents were detected for black currant fruits and jams. Regarding the total phenolic content, in 11 cases it is possible to observe a higher content in jams with respect to the related row fruits. All samples contain a high amount of potassium, calcium and magnesium but small quantities of sodium. Phosphate is abundant especially in currants. As regard jams all results about metals are lower than those obtained for fruits, this is due to the dilution during the preparation of the jams. Multivariate statistical analysis shows that on the basis of obtained analytical results it is possible differentiate not only fruit but also the derived jams. (c) 2005 Elsevier Ltd. All rights reserved.


2007 - Use of HR-NMR for the study of honey adulteration [Abstract in Atti di Convegno]
Lolli, Massimo; Plessi, Maria; Bertelli, Davide; Papotti, Giulia; A. G., Sabatini
abstract

Viene presentato un metodo per la determinazione dell'adulterazione di miele con sciroppi zuccherini commerciali mediante HR-NMR


2006 - Analisi DRIFTS per il riconoscimento di mieli adulterati [Relazione in Atti di Convegno]
Bertelli, Davide; Plessi, Maria; A. G., Sabatini; Lolli, Massimo; G. L., Marcazzan
abstract

La possibilità di riconoscere l’adulterazione del miele con sciroppi zuccherini di diversa origine (cereali, canna da zucchero, barbabietola) è un problema estremamente sentito in apicoltura. A tal fine sono state utilizzate diverse tecniche cromatografiche e spettroscopiche, tra queste a nostro avviso non è mai stata utilizzata la spettroscopia infrarossa in riflettanza diffusa (DRIFTS). Scopo del lavoro è stato quello di verificare quindi la capacità di un metodo, precedentemente da noi sviluppato per il riconoscimento botanico, di discriminare fra campioni di miele adulterati con soluzioni zuccherine commerciali di diverso tipo e campioni di mieli genuini.


2006 - Analisi HR-NMR per la valutazione dello stato ossidativo di grassi animali [Relazione in Atti di Convegno]
Lolli, Massimo; Bertelli, Davide; Plessi, Maria
abstract

L’utilizzo della spettrometria NMR nello studio della componente grassa degli alimenti è sempre più presente in letteratura, in particolare per i grassi di origine vegetale; meno frequenti sono invece i lavori riguardanti i grassi di origine animale. Decisamente scarsi sono gli studi relativi all'impiego quantitativo delle informazioni che si possono ricavare da questa tecnica. Lo scopo del presente lavoro è quello di effettuare una valutazione iniziale sulla possibilità di utilizzo di tecniche di risonanza magnetica nucleare ad alta risoluzione per lo studio dello stato ossidativo di grassi di origine animale, attraverso l’identificazione e successiva quantificazione di prodotti di ossidazione.


2006 - Applicazione della risonanza magnetica nucleare ad alta risoluzione (HR-NMR) per lo studio di alimenti di origine animale. [Relazione in Atti di Convegno]
Bertelli, Davide; Lolli, Massimo; Plessi, Maria
abstract

Vengono presentate alcune applicazioni della risonanza magnetica nucleare ad alta risoluzione allo studio di matrici alimentari di origine anaimale (miele, strutto, prosciutto).


2006 - Determinazione di fruttosio e glucosio nel miele mediante spettroscopia infrarossa in riflettanza diffusa (DRIFTS) [Relazione in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; A. G., Sabatini; Lolli, Massimo; F., Grillenzoni
abstract

La spettroscopia infrarossa in riflettanza diffusa (DRIFTS) associata a metodi di calibrazione multivariata è stata da noi utilizzata per la determinazione contemporanea dei contenuti di fruttosio e glucosio in mieli di diversa origine botanica sia provenienti da diverse regioni italiane che dall’estero; a nostra conoscenza, precedentemente questa tecnica non è mai stata utilizzata sul miele a tale scopo.


2006 - Extraction and identification by GC-MS of phenolic acids in traditional balsamic vinegar from Modena [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; F., Miglietta
abstract

Traditional balsamic vinegar from Modena (Aceto balsamico tradizionale di Modena, ABTM) is a typical Italian product obtained by a traditional method from grape must. As the chemical composition of this vinegar has not yet been fully investigated, the present work aims to develop a method for investigating the presence of biologically active compounds such as phenolic acids. The physico-chernical characteristics of ABTM required the development of a specific method for phenolic acid extraction. Different materials, such as diatomaceous earth cartridges for liquid-liquid extraction and polyamidic SPE cartridges, have been tested. The identification of phenolic acids in extracts of ABTM has been carried out using a GC/MS method after derivatization with bis(trimethylsilyl)trifluoroacetamide (BTSFA). The developed procedure allowed the identification in ABTM of nine phenolic acids, confirming also the presence of these natural antioxidants at the end of the process that transforms grape must into ABTM.


2005 - Headspace solid-phase microextraction-gas chromatography-mass spectrometry analysis of the volatile compounds of Evodia species fruits [Articolo su rivista]
Pellati, Federica; Benvenuti, Stefania; F., Yoshizaki; Bertelli, Davide; Rossi, Maria Cecilia
abstract

In this study the investigation of the aroma compounds of dried fruits of Evodia rutaecarpa (Juss.) Benth. and E. rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang (i.e. E. officinalis Dode) (Rutaceae family) was carried out to identify the odorous target components responsible for the characteristic aroma of these valuable natural products. To avoid the traditional and more time-consuming hydrodistillation, the analyses were carried out by means of headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography–mass spectrometry (GC–MS). The SPME headspace volatiles were collected using a divinylbenzene–carboxen–polydimethylsiloxane (DVB–CAR–PDMS) fiber. The extraction conditions were optimized using a response surface experimental design to analyze the effect of three factors: extraction temperature, equilibrium time and extraction time. The best response was obtained when the extraction temperature was around 80 °C, equilibrium time near 25 min and extraction time close to 18 min. Analyses were performed by GC–MS with a 5% diphenyl–95% dimethyl polysiloxane (30 m × 0.25 mm I.D., film thickness 0.25 μm) capillary column using He as the carrier gas and a programmed temperature run. The main components of the HS-SPME samples of E. rutaecarpa (concentration >3.0%) were limonene (33.79%), β-elemene (10.78%), linalool (8.15%), myrcene (5.83%), valencene (4.73%), β-caryophyllene (4.62%), linalyl acetate (4.13%) and α-terpineol (3.99%). As for E. officinalis, the major compounds were myrcene (32.79%), limonene (18.36%), β-caryophyllene (9.92%), trans-β-ocimene (6.04%), linalool (5.88%), β-elemene (7.85%) and valencene (4.62%).


2005 - Valutazione dei costituenti principali di aceti balsamici tradizionali prodotti nella provincia di Modena [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Miglietta, Francesca
abstract

The composition properties of 14 barrels sets of aged Traditional Balsamic Vinegar were analysed to examine its production in Modena area. Different chemical parameters were valuated: total, fixed and volatile acidity, density, reducing sugars, glycerol and ethanol. Also proline, the main aminoacid in grape, and polyphenols, natural healthful substances with antioxidant properties, were determined. The obtained results showed a significant variability, related to the handmade procedure of vinegar processing. However these results were in agreement with data indicated in the last researches, corresponding to the typical chemical characteristics of this product.


2004 - Analisi DRIFTS per la classificazione di mieli uniflorali [Abstract in Atti di Convegno]
Bertelli, Davide; Plessi, Maria
abstract

E' stato costruito un modello atto a classificare i milei uniflorali mediante analisi spettrofotometrica DRIFTS e successiva analisi chemiometrica dei dati.


2004 - Effect of industrial microwave treatment on the antioxidant activity of herbs and spices [Articolo su rivista]
Bertelli, Davide; Plessi, Maria; F., Miglietta
abstract

The effect of the industrial treatment with microwaves on the antioxidant activity of herbs and spices was evaluated. Samples of black pepper (Piper nigrum L.), oregano (Origanum vulgare L.), basil (Ocimum basilicum L.) and sage (Salvia officinalis L.) obtained before and after the microwave treatment were extracted with an acetone-water mixture (70:30). the extracts were analyzed for their phenolic content. The antioxidant activity was determined using the DPPH (2,2-diphenyl-1-picrylhydrazyl) and deoxyribose methods and the prooxidant activity was determined by evaluating the reducing power and the iron chelating capacity. The treatment did not modify the antioxidant properties of these herbs and spices as the majority of the differences between treated and non treated samples were not statistically significant.


2004 - HS-SPME-GC-MS analysis of the volatile compounds of Evodia species fruits [Abstract in Atti di Convegno]
Pellati, Federica; Benvenuti, Stefania; Bertelli, Davide; F., Yoshizaki; Rossi, Maria Cecilia
abstract

In this study, a HS-SPME-GC-MS method for the analysis of the volatile compounds of Evodia species fruits was developed.


2004 - Polyphenols, anthocyanins, ascorbic acid, and radical scavenging activity of Rubus, Ribes, and Aronia [Articolo su rivista]
Benvenuti, Stefania; Pellati, Federica; M., Melegari; Bertelli, Davide
abstract

Total polyphenols, total anthocyanins, and reduced ascorbic acid were evaluated in berries belonging to the genera Rubus, Ribes, and Aronia by means of spectrophotometric and HPLC techniques.The 2,2-diphenyl-1-picrylhydrazyl (DPPH•) radical scavenging activity of the fruit extracts was tested. Total polyphenols ranged from 140.6 to 888.5 mg/100 g fresh weight (FW), total anthocyanins ranged from 22.0 to 460.5 mg/100 g FW, and reduced ascorbic acid ranged from 12.4 to 153.8 mg/100 g FW. The average EC50 values for A. melanocarpa, R. nigrum, R. rubrum, R. fruticosus and R. idaeus were 1.8, 2.8, 5.3, 6.4 and 8.2 mg FW, respectively. The results indicate that the fruits tested are good sources of natural antioxidants.


2003 - Effect of microwaves on volatile compounds in origanum [Articolo su rivista]
Bertelli, Davide; Plessi, Maria; F., Miglietta
abstract

A headspace-solid-phase microextraction-capillary gas-chromatography method was used to evaluate the effect of microwave treatment on volatile compounds of origanum (Origanum vulgare L.). The extraction of volatile compounds was performed using a 50/30 divinylbenzene/carboxen on polydimethylsiloxane on a 2 cm StableFlex fiber (Supelco). The most significant chromatographic peaks were identified using standard materials and GC-MS analysis. The analyses were conducted on samples, treated and non-treated with microwaves, coming from two different types of origanum. The results obtained were submitted to univariate and multivariate statistical analysis. Data obtained allowed to identify the principal differences between the two types of origanum and showed that type 1 (thymol/carvacrol chemotype) is less influenced by microwave treatment than type 2 (carvacrol chemotype). Considering the most important components for origanum aroma, thymol and carvacrol, the differences found are only marginally significant between treated and non-treated samples of all types of origanum considered. (C) 2003 Swiss Society of Food Science and Technology. Published by Elsevier Science Ltd. All rights reserved.


2003 - Valore nutrizionale della corniola, frutto del Cornus Mas L. [Relazione in Atti di Convegno]
Bertelli, Davide; Plessi, Maria; Miglietta, Francesca
abstract

Vengono riportati i risultati relativi all'analisi del valore nutrizionale del Corniolo, nonchè di alcuni componenti funzionali quali fibra dietetica e sostanza fenoliche.


2003 - Valutazione dell'attività antiossidante di aceti balsamici [Relazione in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Miglietta, Francesca
abstract

L'attività antiossidante di campioni di Aceto balsamico tradizionale di Modena e di Aceto balsamico di Modena nonchè il contenuto di sostanze fenoliche sono stati valutati mediante metodi in vitro e spettrofotometrici.


2002 - Effect of microwaves on volatile compounds in white and black pepper [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; F., Miglietta
abstract

A head space-solid-phase micro extraction-capillary gas-chromatography method was developed to evaluate the effect of microwave treatment on volatile compounds of white and black Pepper (Piper nigrum L.). The extraction of volatile compounds from the head space was performed using a 50/30 divinylbenzene/Carboxen on a 2 on StableFlex fibre (Supelco). The GC-MS analysis and standards allowed the identification of most substances extracted from fumes. The GC analyses were conducted on 12 samples each of white and black pepper treated and nontreated with microwave; these samples were provided by Cannamela(R). The results obtained were subjected to statistical analysis, which shows that only small differences existed between treated and nontreated samples; these differences seem unable to produce a real differentiation between samples. Therefore, it is possible to conclude that the microwave treatment seems to preserve the principal aroma compounds of white and black pepper.


2002 - Identificazione di acidi fenolici nell'aceto balsamico tradizionale di Modena [Abstract in Atti di Convegno]
Miglietta, Francesca; Bertelli, Davide; Plessi, Maria
abstract

Applicazione di un metodo per estrazione, purificazione e quantificazione mediante RP-HPLC di acidi fenolici in aceto balsamico tradizionale di Modena (ABTM).


2002 - Metalli in tracce in spezie ed in prodotti erboristici [Abstract in Atti di Convegno]
C., Ggigliotti; Plessi, Maria; Bertelli, Davide
abstract

Studio del contenuto in metalli in tracce in campioni di spezie e prodotti erboristici presenti sia nei punti vendita non convenzionali che convenzionali mediante GFAAS.


2001 - Estrazione e frazionamento di sostanze fenoliche in aceti balsamici. (Extraction and fractionation of polyphenol substances in Balsamic vinegars). [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; F., Miglietta
abstract

Balsamic vinegar of Modena is a typical product made from grape must by traditional prodn. method with extensive aging. The presence of biol. active polyphenol components in the vinegar was studied using a modified extn. method. Several extn. procedures and solvents (Et acetate, 4-methylpentan-2-one, isoamyl alc., n-butanol) were tested. The total phenols in exts. were detd. with the Folin-Ciocalteu reagent and expressed as gallic acid contents. The phenolic substances were then fractionated on C18 solid-phase extn. cartridges into neutral and acidic compds. and expressed as gallic acid and (+)-catechin contents, resp.


2001 - Indagine conoscitiva per la determinazione della componente polifenolica nell'aceto balsamico tradizionale di Modena [Abstract in Atti di Convegno]
Miglietta, Francesca; Bertelli, Davide; Plessi, Maria
abstract

Messa apunto di metodi per l'estrazione, purificazione e detreminazione della componente fenolica dell'aceto balsamico tradizionale di Modena


2001 - Mercury and selenium contents in selected seafood [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

The mercury and selenium contents of fresh seafood were determined, respectively, by means of cold vapor atomic absorption spectroscopy (CVAAS) and hydride-generation atomic absorption spectrometry (HGAAS). All the values obtained were lower than the European Union´s legal limit of 0.5 mg/kg fresh food, rising to 1.0 mg kg for the edible parts of some listed species; in fish they vary between 0.057 mg/kg in sole and 0.579 mg/kg in swordfish (included in the category of large fish, for which the legal limit is 1 mg/kg). The levels of selenium vary between 0.073 mg/kg in perch and 0.743 mg/kg in tuna. In shellfish the mercury content varies between 0.023 mg/kg in moscardino and 0.150 mg/kg in Mediterranean shrimp, while that of selenium varies between 0.067 mg/kg in spiny lobster and 0.605 mg/kg in mussels. A significant difference was found between fish and shellfish for mercury, but not for selenium. A large excess of selenium in relation to mercury was observed (the mean molar ratio of Hg/Se is 0.23 for fish and 0.09 for shellfish), but no significant correlation was found between the two elements.


2000 - Approccio chemiometrico all'ottimizzazione della mineralizzazione a microonde per la determinazione di alluminio mediante GFAAS. [Relazione in Atti di Convegno]
Bertelli, Davide; Plessi, Maria; Monzani, Agar
abstract

Criteri chemometrici sono stati applicati all'ottimizzazione del trattamento a MW utilizzato per mineralizzare la matrice nella determinazione di Al in tracce in alimenti.


2000 - Effetto delle microonde sulla componente polifenolica e sull'attività antiossidante di Origanum Vulgare [Relazione in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

E' stato verificato l'efetto di un trattamento di sanificazione a microonde sul contenuto di sostanze polifenoliche e sull'attività antiossidante di origano.


1999 - Determinazione della frazione aromatica in frutti di mirto [Relazione in Atti di Convegno]
Bertelli, Davide; Albasini, Albano
abstract

L'analisi della frazione volatile delle bacche di mirto è stata svolta mediante l'impiego le tecniche HS-SPME-GC e HS-SPME-GCMS ed ha permesso di dosare una trentina di composti volatili.


1999 - Dietary fiber and some elements in nuts and wheat brans [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Monzani, Agar; Ms, Simonetti; A., Neri; P., Damiani
abstract

The contents of some elements in nuts and commercial dietary wheat brans were evaluated. In nuts and TDF residues, Ca, Mg, Zn, Fe and Cu were determined. In commercial bran-based foods produced for five years, toxic (Pb and Cd) and two nutritionally important (Cu and Zn) metals were determined. The percentage of elements in fiber varied significantly among fiber sources. The content of toxic metals in the dietary wheat bran-based products investigated is very low (0.074 mg/kg for Cd and 0.161 mg/kg for Pb). Regarding the samples of dietary wheat bran, a significant variation during the time is observed only for Cd content.


1999 - La castagna un frutto dell’appennino: composizione e caratteristiche nutrizionali. (Chestnut from Emilian appennines: proximate analysis and nutritional value) [Articolo su rivista]
Plessi, Maria; Bertelli, Davide
abstract

Chestnut, yhe fruit of castanea sativa Mill., are typical products of the Italian mountain regions and also of the Tuscan-emilia appennines. Therefore, some samples of chestnuts from Zocca (Modena) were analyzed to determine proximate analysis and other parameter usable to asses the global quality of the product. Chestnuts show high content of starch, sugars and dietary fiber. as regards mineral content, appreciable amounts are those of calcium and magnesium. Also the relationships between dietary fiber and mineral are interesting.


1998 - Analisi di macro e micro elementi in frutti dei generi ribes, rubus e vaccinium e in confetture da essi ottenute [Relazione in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Albasini, Albano
abstract

Campioni di frutta e confetture sono stati analizzati mediante ICPES per la determinazione di macro e micro elementi.


1998 - Fruits of ribes, rubus, vaccinium and prunus genus. Metal contents and genome [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Rastelli, Giulio; Albasini, Albano; Monzani, Agar
abstract

The production of fruits of genus Ribes, Rubus, Vaccinium and Prunus is particularly important in mountain communities. The contents of macro- and microelements in fruits from different cultivars of blueberry (Vaccinium corimbosus L.), red currant (Ribes rubrum L.), raspberry (Rubus idaeus L.) and cherry (Prunus avium L.) were determined. The anthocyanin and total polyphenol contents of the fruits were also determined. The results were analyzed with statistical methods. By using the one-way analysis of variance (ANOVA) the various genera of the fruits were found to be differentiable on the basis of their metal contents. Multivariate statistical analysis, performed using principal component analysis (PCA), confirms that the different fruits can also be well discriminated by their contents of metals, total anthocyanins, and polyphenols.


1998 - Impiego della gascromatografia-spettrometria di massa per la valutazione della patulina in matrici alimentari [Abstract in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

E' stato sviluppato un metodo per la determinazione della patulina, micotossina a basso PM, in prodotti a base di frutta mediante GC-MS.


1998 - Separation by solid phase extraction and quantification by reversed phase HPLC of sulforaphane in broccoli [Articolo su rivista]
Bertelli, Davide; Plessi, Maria; Braghiroli, Daniela; Monzani, Agar
abstract

The separation and quantification of sulforaphane [1-isothiocyanato-4-(methylsulfinyl)-butane] from the florets, stalks and leaves of broccoli is described. The procedure uses solvent extraction, followed by purification of extracts using solid phase extraction (SPE) and reverse phase HPLC analysis. The HPLC method is compared with a spectrophotometric assay. To obtain information about the usefulness of acid hydrolysis of glucosinolates, the florets were left to autolyze at room temperature or were treated with concentrated hydrochloric acid, then analysed. The method proves reliable and reproducible as regards both SPE purification and chromatographic determination. Quantities of sulforaphane were found in the florets, stalks and leaves. The highest content of sulforaphane (110 mu g g(-1)) was found in the leaves. (C) 1998 Elsevier Science Ltd. All rights reserved.


1998 - Valutazione del contenuto di patulina in prodotti per la prima infanzia a base di mela (Determination of patulin in apple-based infant foods). [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

Patulin in apple-based infant food was detd. by solvent extn. followed by solid phase extn. for sample clean up and reversed-phase HPLC on a Lichrospher 100 RP-18 column. Patulin was found in some samples, but below WHO tolerances (50 .mu.g/L). The highest content (4.96 .mu.g/L) was found in a sample of apple and banana sauce; the lowest (0.12 .mu.g/L) was found in apple juice. The limit of detection was 3.1 .mu.g/L.


1997 - Determination of aluminium and zinc in infant formulas and infant foods [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

Seven different infant formulas and 18 different types of infant foods representative of infant diets in italy were analyzed to gain further information about the composition of infant diets, with particular reference to Al and Zn intake. after a microwave mineralization pretreatment, Al


1997 - Fruit of ribes, rubus, vaccinium and prunus genus, metals content and genome [Abstract in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Rastelli, Giulio; Albasini, Albano; Monzani, Agar
abstract

The metal content of fruits of genus rubus, ribes, vaccinium and prunus has been determined by indictively coupled plasma emission spectrometry


1997 - Indagine sul contenuto di sulforafano nelle crucifere alimentari mediante messa a punto di uno specifico metodo analitico [Abstract in Atti di Convegno]
Bertelli, Davide
abstract

Il lavoro riguarda la messa a punto ed applicazione di un metodo per l'estrazione e la quantificazione di sulforafano in crucifere alimentari.


1997 - Influence of seafood and canned seafood on mercury and selenium intake [Abstract in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

Influence of seafood and canned seafood on mercury and selenium intake was evaluated measuring Hg and Se by CVAAS and HGAAS.


1997 - Sostanze di natura polifenolica e minerali in frutti del genere Prunus e loro prodotti di trasformazione (Polyphenolic substances and minerals in Prunus genus fruits and products of their processing). [Articolo su rivista]
Plessi, Maria; Bertelli, Davide; Albasini, Albano
abstract

Cherry from Prunus cerasus is widely used for its well known properties. The most important Italian area for cherry prodn. is the country around Vignola (Modena). The very short period of harvesting and the difficult preservation, require that a large amt. of fresh fruits is transformed in preserves and jams. We detd. the content of polyphenolic compds. in fresh cherries, cherry jams, and some com. jams to show the presence of compds. with high pharmacol. activity and potential beneficial effects on health. Micromineral (Zn, Fe, Mn) and macromineral (Ca, Mg, P, Na, K) nutrients were also detd. The polyphenol content in cherries was sufficiently high and the processing to jams did not cause many changes. The anthocyanidins were practically absent in com. jams. The cherries contained sufficient amts. of Ca and P, high levels of K, and low levels of Na.


1997 - Tannini e minerali in peperoncini di varia origine [Abstract in Atti di Convegno]
Plessi, Maria; Bertelli, Davide; Monzani, Agar
abstract

Sono stati valutati polifenoli totali, tannini, macro e microelementi in peperoncini di diversa origine mediante tecniche spettrofotometriche.


1996 - Studio analitico della fibra dietetica in frutti dell'appennino modenese [Abstract in Atti di Convegno]
Plessi, Maria; Avallone, Rossella; Bertelli, Davide; Monzani, Agar
abstract

Nuts and chestnuts were analized for SDF and IDF using AOAC official method. Pectins, cellulose, hemicellulose and lignin were also evaluated.


1995 - Aluminium levels in baby foods determined by electrothermal atomic absorption spectrometry. [Relazione in Atti di Convegno]
Plessi, Maria; Monzani, Agar; Bertelli, Davide
abstract

Aluminium content of different infant foods and formulae were determined by ETAAS after microwave assisted wet digestion.