Carmelo García Barroso

Study of the polyphenol content of red and white grape varieties by liquid chromatography-mass spectrometry and its relationship to antioxidant power

There is considerable interest in the analysis of phenolic compounds due to their involvement in the organoleptic characteristics of foods and drinks, and their contribution to protection against cardiovascular diseases and cancers through their antioxidant activity. This article describes studies of the polyphenol content, both total (by means of the Folin-Ciocalteu method) and individual (by means of HPLC, LC-MS and LC-MS-MS) and the antioxidant power, of six varieties of grape over the course of their maturation. A good correlation is found to exist between the total polyphenol content of the samples and their antioxidant power, and both seem diminish along the maturation.

Optimisation of headspace solid-phase microextraction for the analysis of volatile phenols in wine

Headspace solid-phase microextraction has been applied to the analysis of volatile phenols in wine. Silica fibre coated with Carbowax-divinylbenzene was found to be more efficient at extracting these compounds than other fibres such as those coated with polydimethylsiloxane, polyacrylate, carboxen-polydimethylsiloxane, and polydimethylsiloxane-divinylbenzene. Different parameters such as extraction time, temperature of the sample during the extraction, ionic strength and sample volume were optimised using a two-level factorial design expanded further to a central composite design, in order to evaluate several possibly influential and/or interacting factors. The headspace (HS)-SPME procedure developed shows adequate detection and quantitation limits, and linear ranges for correctly analysing these compounds in wine. The recoveries obtained were close to 100%, with repeatability values lower than 16%. The method was applied to a variety of white and red wines.

Optimisation of headspace solid-phase microextraction for analysis of aromatic compounds in vinegar.

Abstract Headspace solid-phase microextraction has been applied to the analysis of aroma compounds in vinegar. Silica fibre coated with Carboxen–polydimethylsiloxane was found to be more efficient at extracting these compounds than other fibres such as those coated with polydimethylsiloxane, Carbowax–divinylbenzene, and polydimethylsiloxane–divinylbenzene, but its repeatability was low. Different parameters such as extraction time, temperature of the sample during the extraction, ionic strength, and sample volume were optimised using a two-level factorial design expanded further to a central composite design. This chemometric tool is very appropriate in screening experiments where the aim is to investigate several possibly influential and/or interacting factors. The extraction efficiency is inversely affected by the acetic acid content—an increase in the acetic acid concentration decreases the extraction efficiency. No interference is observed with the increase in content of polyphenols.

Headspace solid-phase microextraction analysis of aroma compounds in vinegar. Validation study.

Headspace solid-phase microextraction (HS-SPME) was evaluated for analysing aromatic compounds in vinegar. The fibre used (a Carboxen-polydimethylsiloxane fibre), and the analytical conditions had been optimised in a previous work. The HS-SPME procedure developed shows detection and quantitation limits, and linear ranges adequate for analysing this type of compounds. The recoveries obtained were close to 100%, with repeatability values lower than 20%. However, considerable differences have been detected between different fibres. The method was applied to a variety of Sherry wine vinegars.

Development of a stir bar sorptive extraction method coupled to gas chromatography-mass spectrometry for the analysis of volatile compounds in Sherry brandy

Sherry brandy (Jerez, SW, Spain) is a high quality distilled beverage derived from wine. Its perceived quality depends, inter alia, on hundreds of flavour compounds. A Stir Bar Sorptive Extraction (SBSE) method coupled to gas chromatography-mass spectrometry has been developed for the analysis of volatile compounds in Sherry brandy. The optimization of the extraction procedure has been carried out using a statistical approach, based on a factorial design. The best overall analytical conditions obtained were the following: 35 mL of sample, diluted 1:1 with Milli-Q water and extraction at 1100 rpm for 100 min. The method has been successfully validated in a further stage of this work. Several performance characteristics such as calibration, linearity, precision (inter- and intra-assay), detection and quantification limits and recovery were studied. Finally, the method developed has been applied to different Sherry brandies. The results obtained show SBSE to be a suitable technique for the reliable analysis of volatile compounds in brandies.

Study of the polyphenolic composition and antioxidant activity of new sherry vinegar-derived products by maceration with fruits.

Several experiments of maceration of a sherry wine vinegar with different fruits (orange, lemon, strawberry, grapefruit, and lime) have been carried out. After optimization (only peel, no heating and seven days as maximum time of maceration), parameters such as polyphenolic content, superoxide anion scavenging ability (related to antioxidant activity) and ascorbic acid content were determined in sherry wine vinegars macerated with two amounts of peel and for two maceration times (3 and 7 days). The analysis of variance pointed to a clear relationship (p<0.01) between type of fruit and amount of peel and polyphenolic content. The factor time was practically not significant for any polyphenol. Sherry wine vinegars macerated with different fruits exhibited higher superoxide anion scavenger ability, with the maximum values found for the vinegar macerated with lemon peel. The correlation analysis showed that the superoxide anion scavenger ability of the vinegars macerated, and thus their antioxidant activity, was highly correlated (p<0.01) with several polyphenols, especially with naringin, hesperidin, neohesperidin and gentisic acid and not with the ascorbic acid content.

A new FT-IR method combined with multivariate analysis for the classification of vinegars from different raw materials and production processes.

BACKGROUNDnDue to the diversity of vinegars on the market and the increase in demand, it is considered necessary to investigate and establish criteria for classifying them in order to obtain more information concerning their real origin. New spectroscopic techniques such us mid-infrared spectroscopy with Fourier transform (FT-IR) are capable of providing information in relation to these aspects. FT-IR combined with multivariate analysis has been used to classify vinegars according to the raw materials and production processes (with or without ageing in wood). Principal component analysis (PCA), partial least-squares discriminant analysis regression (PLS-DA) and stepwise linear discriminant analysis (SLDA) were used.nnnRESULTSnThe results obtained have been compared to those achieved using different analytical parameters (polyphenolic content, organic acids and volatile compounds). SLDA and PLS-DA results show the ability of mid-FT-IR spectra to discriminate among vinegars from different raw materials and with or without ageing in wood, with correct classification percentages similar to those obtained using different analytical parameters.nnnCONCLUSIONnThe discriminative ability combined with other advantages (e.g. rapid and non-destructive analysis, low cost) makes this new FT-IR method a promising tool for the classification and/or differentiation of vinegars.

Characterization and Differentiation of Sherry Brandies Using Their Aromatic Profile

Aroma compounds of 48 Sherry brandies have been identified and quantified by the stir bar sorptive extraction method coupled to gas chromatography-mass spectrometry (SBSE-GC/MS). Analysis of variance and multivariate analysis techniques have been used to classify these brandy samples according to the commercial category (Solera brandy, Solera Reserva brandy, and Solera Gran Reserva brandy). From an univariate point of view (analysis of variance), several of the volatile compounds considered showed significant differences. Principal component analysis, using the global data matrix, showed that only the Solera brandy samples, with the shortest aging in wood, were well-differentiated from the others. Partial least-squares discriminant analysis (PLS-DA) results provided evidence of the ability of the content of volatile compounds to discriminate among the different commercial categories. Linear discriminate analysis allowed for a 93% differentiation according to the commercial category and, thus, the length of its aging process in wood. The results obtained show that it would be possible to ensure the commercial category of a Sherry brandy using its content of volatile compounds.

Analysis of sugar acids by capillary electrophoresis with indirect UV detection. Application to samples of must and wine.

Abstract. A study has been conducted of the separation of sugar acids (gluconic, galacturonic and glucuronic acids) by capillary electrophoresis using indirect UV detection. We have tested various background electrolytes: p-hydroxibenzoic acid, sorbic acid, potassium hydrogen phthalate, protocatechuic acid, α-resorcylic acid and β-resorcylic acid. The choice between these electrolytes was made on the basis of studies of electrophoretic mobility and absorbance values at the wavelengths of our CE system. Of all the electrolytes tested, it was found that β-resorcylic acid best met the required characteristics. The best separation of the three acid was achieved with a time of 8xa0min, for an electrolyte consisting of 5xa0mM β-resorcylic acid, 1xa0mM TTAOH (pH 3.0), indirect detection at 214xa0nm, -20xa0kV of run voltage and capillary of 60xa0cm length and 75 µm i.d. It was found that the proposed method is applicable to samples of both must and wine, and that the samples do not require any prior treatment apart from centrifugation (only in the case of must), filtration and dilution in suitable proportion.

Optimizing the process of making sweet wines to minimize the content of ochratoxin A.

During the drying process of raisins, the grapes are subjected to climatic variations that can result in heavy infections of some fungal species that produce ochratoxin A (OTA), a powerful toxic metabolite, whose maximum permitted content is set by the European Union at 2.0 μg/L for grapes, wine and other drinks derived from the grape. The aim of this paper is to optimize the process of making sweet wines in order to minimize the content of ochratoxin A. The results reflect a reduction of the OTA content in grapes dried under controlled conditions in a climatic chamber up to 24% compared to those sunned in the traditional way. A decrease of the concentrations of OTA is also observed during the processes of vinification. Those wines with prefermentative maceration reached a higher OTA content than the wines without maceration, but unexpectedly were not those preferred from a sensorial point of view. In addition, the process of aging in oak casks has been shown to serve as a natural method for reducing the OTA content of these wines.