Sandra Pati

Verbascoside, Isoverbascoside, and Their Derivatives Recovered from Olive Mill Wastewater as Possible Food Antioxidants

Olive oil processing industries generate substantial quantities of phenolic-rich byproducts, which could be valuable natural sources of antioxidants. This work is focused on the recovery and structural characterization of antioxidant compounds from olive mill wastewater (OMWW), a polluting byproduct of the olive oil production process. Phenolics were extracted from the waste material using a membrane technology coupled to low-pressure gel filtration chromatography on a Sephadex LH-20. The LH-20 fraction was, in turn, characterized for its phenolic composition by HPLC-DAD-MS/MS analyses. Verbascoside, isoverbascoside, β-hydroxyverbascoside, β-hydroxyisoverbascoside, and various oxidized phenolics were identified. Uptake of verbascoside, purified from the LH-20 fraction, by HT-29 cells, an established model system for studying drug transport properties, was also assayed. Finally, the antioxidant activities of the LH-20 fraction and verbascoside were characterized by two different techniques. Individual verbascoside was more active as a scavenger of reactive oxygen species and as a chemopreventive agent protecting low-density lipoproteins from oxidative damage than the LH-20 fraction.

Rapid screening for anthocyanins and anthocyanin dimers in crude grape extracts by high performance liquid chromatography coupled with diode array detection and tandem mass spectrometry

A rapid and efficient method using high performance liquid chromatography coupled with diode array detection and tandem mass spectrometry (HPLC-DAD-MS/MS) for fast screening large numbers of anthocyanins and anthocyanin dimers in different grape skin extracts, without further sample clean-up procedures, was developed. A good separation of most detected anthocyanins was achieved in a run time of 15 min. Identification of anthocyanin pigments required a combination of several information: UV-vis spectra, MS and MS/MS spectra, and elution pattern. Many compounds have been here detected for the first time and their structures tentatively elucidated.

Biological Activity of High Molecular Weight Phenolics from Olive Mill Wastewater

Olive oil production generates large amounts of recalcitrant compounds, the olive oil mill wastewater (OMWW), which represent one of the most contaminating effluents among those produced by the agrofood industries. Nowadays, this view has changed to one that recognizes the waste as a low-cost starting material rich in bioactive compounds, particularly biophenols, that can be extracted and applied as natural antioxidants for the food and pharmaceutical industries. The data reported in this paper indicate that the OMWW extracts, besides low molecular weight antioxidant phenolics such as tyrosol and hydroxytyrosol, also contain phenolics with a molecular weight in the range of 600-5000 Da, which exhibit efficient scavenging activities against hydroxyl and peroxyl radicals. This group of phenolics includes, besides verbascoside, isoverbascoside, and an oxidized form of verbascoside, a number of higher molecular weight phenolics arising from oxidative polymerization of hydroxytyrosol and caffeic acid. Overall, these higher molecular weight phenolics prove to be, in some in vitro tests, more efficient scavengers of hydrophilic hydroxyl radicals than hydroxytyrosol, which could be used for industrial applications as natural nontoxic antioxidants.

Acaricide Residues in Laying Hens Naturally Infested by Red Mite Dermanyssus gallinae

In the poultry industry, control of the red mite D. gallinae primarily relies worldwide on acaricides registered for use in agriculture or for livestock, and those most widely used are carbamates, followed by amidines, pyrethroids and organophosphates. Due to the repeated use of acaricides - sometimes in high concentrations - to control infestation, red mites may become resistant, and acaricides may accumulate in chicken organs and tissues, and also in eggs. To highlight some situations of misuse/abuse of chemicals and of risk to human health, we investigated laying hens, destined to the slaughterhouse, for the presence of acaricide residues in their organs and tissues. We used 45 hens from which we collected a total of 225 samples from the following tissues and organs: skin, fat, liver, muscle, hearth, and kidney. In these samples we analyzed the residual contents of carbaryl and permethrin by LC-MS/MS. Ninety-one (40.4%) samples were positive to carbaryl and four samples (1.7%) were positive to permethrin. Concentrations of carbaryl exceeding the detection limit (0.005 ppm) were registered in the skin and fat of birds from two farms (p<0.01), although these concentrations remained below the maximum residue limit (MRLs) (0.05 ppm) (p<0.01). All organs/tissues of hens from a third farm were significantly more contaminated, with skin and muscle samples exceeding the MRL (0.05 ppm) (p<0.01) of carbaryl in force before its use was banned. Out of 45 chickens tested, 37 (82.2%) were found to be contaminated by carbaryl, and 4 (8.8%) by permethrin. The present study is the first report on the presence of pesticides banned by the EU (carbaryl) or not licensed for use (permethrin) in the organs and tissues of laying hens, which have been treated against red mites, and then slaughtered for human consumption at the end of their life cycle.

Influence of Training System on Volatile and Sensory Profiles of Primitivo Grapes and Wines

The enhancement of grape aroma and the investigation of the relationships between grape and wine composition are important given the growing interest in wines with distinctive varietal character. Each training system involves specific grapegrowing conditions, which affect the concentration of volatile metabolites of grape. The aim of this work was to evaluate the influence of three training systems, including little tree, bilateral Guyot, and four rays, on the volatile composition of Primitivo grape and on the volatile composition and sensory properties of the corresponding wine in Apulia region of Italy. Free and bound volatile fractions were evaluated by gas chromatography coupled to mass spectrometry. Sensory analysis was performed by a panel of trained judges. Results showed that the little tree and bilateral Guyot training systems improved the accumulation of aroma precursors and volatile compounds in grape and wine and the sensory characteristics of the wine.

Effect of harvest time on table grape quality during on-vine storage

BACKGROUND Postponing the harvest of grapes is a common practice in southern Italy, in order to delay harvest up to Christmas and make higher income from their sale. The aim of this work was to evaluate the effect of harvest time (over almost 3 months) on the quality of table grapes (cv. Italia). The experiment was repeated for two years (2010 and 2011). In 2010, grapes were harvested starting from 8 October and after 11, 27 and 48 days. In 2011, five harvest times were compared over a period of 56 days. Respiration rate, firmness, colour, sensory attributes, total soluble solids (TSS), pH, titratable acidity (TA), phenols and antioxidant activity were measured. In addition, in the second year, volatile compounds were evaluated. RESULTS For both years, harvest time influenced most parameters, which indicated that metabolic changes took place in the plants. In 2010, harvest time influenced respiration rate, cluster and berry appearance scores, colour attributes, crunchiness, pH, TA, total phenol content and antioxidant activity. In 2011, harvest time influenced respiration rate, colour attributes, most sensory attributes, TSS and TA. Generally, late harvested grapes showed higher firmness, berry appearance score, sweetness, fruity taste, overall sensory evaluation score and TSS. Regarding volatile compounds, terpene content decreased during ripening, while C6 compounds showed a nonlinear trend. CONCLUSION The results showed that table grape sensory quality could be increased by delaying harvest up to a certain time of the season, while excessive delay could reduce final grape quality.

Study of proteolysis in river buffalo mozzarella cheese using a proteomics approach

The guarantee of the origin and quality of raw material is essential for the protection and valorization of Campana buffalo mozzarella cheese. The risk of utilization of semifinished products and stored milk in substitution for fresh milk is increasing, due to the continuous desire to reduce production costs. A proteomics approach and electrophoresis survey of retail mozzarella cheeses indicated different rates of proteolysis in the production of dairy industries. The use of fresh milk and correct cheesemaking protocol yielded only γ-caseins, which are derived from β-casein by plasmin, and para-κ-casein, which is derived from κ-casein by chymosin. The detection of abnormal hydrolysis resulting in β- and αS1-casein fragments, identified by mass spectrometry, indicates the use of stored milk or stored and pressed curd, or the reuse of unsold mozzarella cheese, to produce mozzarella. The formation of γ-caseins and other fragments during a long storage of raw materials at room or refrigeration temperature was ascribed to plasmin (endogenous milk enzyme), whereas formation of αS1-casein fragments, mainly αS1-I(6P)- and αS1-I(7P)-casein during the storage of curd was ascribed to the action of chymosin (exogenous enzyme) from rennet. Sodium dodecyl sulfate-PAGE and alkaline urea-PAGE permitted us to evaluate the freshness of the raw materials used in the manufacturing of buffalo mozzarella cheese and to reveal possible inappropriate preservation.

Use of microfungi in the treatment of oak chips: possible effects on wine.

BACKGROUND Oak barrels are commonly used in the aging of wines and spirits because of their positive effects on the product. In recent years the addition of oak chips has been used to introduce desirable wood aromas and flavours into wines. In this study, oak chips in saline solution or laboratory medium were inoculated with Penicillium purpurogenum, Aureobasidium pullulans, Phialemonium obovatum, Phanerochaete chrysosporium and a combination of Ph. chrysosporium and A. pullulans. After 12 weeks of incubation, oak chips (2 g L(-1)) were macerated in a red wine for 17 days. Gas chromatography/mass spectrometry and high-performance liquid chromatography were used to evaluate 14 compounds, namely furfural, furfuryl alcohol, guaiacol, syringol, cis-β-methyl-γ-octalactone, 2-phenylethanol, 4-vinylguaiacol, benzyl alcohol, 2,3-butanediol, γ-butyrolactone, benzaldehyde, 4-ethylguaiacol, gallic acid and ellagic acid. RESULTS The microfungal treatments increased the concentration of some components. In particular, P. purpurogenum resulted in a significant improvement in the levels of guaiacol, furfural, syringol, furfuryl alcohol and 2-phenylethanol. CONCLUSION Penicillium purpurogenum and Ph. chrysosporium showed a constant trend (enrichment of furfural and benzaldehyde) independent to some extent of the medium used for chip treatment.

Polysaccharide and volatile composition of Cabernet wine affected by different over-lees ageing

The influence of different over-lees ageing conditions on the soluble polysaccharides’ glycosyl residue and volatile composition of Cabernet wine was addressed in this work. Specific operating conditions have been considered: wine ageing on fine white lees, wine ageing on fine red lees, wine ageing on fine second-passage white lees and short ageing on rough red lees, which were compared with ageing without lees. The ageing on lees led to an increase in all wine polysaccharide glycosyl residues, with the exception of glucose, xylose and myo-inositol, and to volatile profile modifications. Different behaviours could be observed between the four types of lees, giving important hints for a rational use of them in winemaking. In particular, the use of red grape-derived lees caused the major release of polysaccharides; on the other hand, white grape-derived lees were more effective in enhancing ester content. Second-passage lees did not lead to any increase in wine polysaccharides, whereas they allowed aroma changes, and short ageing on rough red lees caused the greatest adsorption of several volatiles.

Electronic nose and GC-MS to investigate the volatile component of an italian traditional pasta

The present work investigated the possibility of combining headspace sampling–solid-phase microextraction with gas chromatography–mass spectroscopy (GC-MS) analysis and an array of semiconductor gas sensors to study the volatile fraction of traditional Italian cereal foods. In particular, it studied a pasta recognized as typical by the Italian laws and made with a semolina obtained from a toasted durum wheat. The GC-MS analysis allowed the identification of several volatile compounds, almost always in small concentrations, in raw materials and in fresh and dried pasta. The data deriving from the application of the GC-MS and electronic nose analyses were submitted to principal component analysis to evaluate the suitability of these techniques for emphasizing differences due to composition and/or processing. These preliminary results showed that both the analytical techniques allowed good discrimination among the meals but not among the pasta samples. RESEARCH