Francisco J. Rodríguez-Pulido

Determination of technological maturity of grapes and total phenolic compounds of grape skins in red and white cultivars during ripening by near infrared hyperspectral image: A preliminary approach

Hyperspectral images of intact grapes during ripening were recorded using a near infrared hyperspectral imaging system (900-1700 nm). Spectral data have been correlated with grape skin total phenolic concentration, sugar concentration, titratable acidity and pH by modified partial least squares regression (MPLS) using a number of spectral pre-treatments and different sets of calibration. The obtained results (RSQ and SEP, respectively) for the global model of red and white grape samples were: 0.89 and 1.23 mg g(-1) of grape skin for total phenolic concentration, 0.99 and 1.37 °Brix for sugar concentration, 0.98 and 3.88 g L(-1) for titratable acidity and for pH 0.94 and 0.12. Moreover, separate calibration models for red and white grape samples were also developed. The obtained results present a good potential for a fast and reasonably inexpensive screening of these parameters in intact grapes and therefore, for a fast control of technological and phenolic maturity.

Comprehensive Colorimetric Study of Anthocyanic Copigmentation in Model Solutions. Effects of pH and Molar Ratio

New colorimetric variables have been defined in the uniform CIELAB color space to assess the quantitative and qualitative color changes induced by copigmentation and their incidence on visual perception. The copigmentation process was assayed in model solutions between malvidin 3-glucoside and three phenolic compounds (catechin, epicatechin, and caffeic acid) as a function of the pH and the pigment/copigment molar ratio. Along the pH variation, the greatest magnitude of copigmentation was obtained at pH 3.0, being significantly higher with epicatechin and caffeic acid. At high acidic pH, the main contribution of copigmentation to the total color was qualitative, whereas between pH 2.0 and 4.0, the main colorimetric contribution was quantitative. The contribution of epicatechin and caffeic acid to the color changes was more marked for the quantitative characteristics. On contrast, particularly at higher pH values, the qualitative contribution was more important in catechin copigmented solutions. Increasing copigment concentration induced perceptible color changes at molar ratios higher than 1:2, consisting in a bluish and darkening effect of the anthocyanin solutions. Among the different CIELAB attributes, hue difference was the best correlated parameter with the increase of copigment concentration, proving the relevance of this physicochemical phenomenon on the qualitative changes of anthocyanin color.

Feasibility Study on the Use of Near-Infrared Hyperspectral Imaging for the Screening of Anthocyanins in Intact Grapes during Ripening

The potential of near-infrared hyperspectral imaging to determine anthocyanins in intact grape has been evaluated. The hyperspectral images of intact grapes during ripening were recorded using a near-infrared hyperspectral imaging covering the spectral range between 900 and 1700 nm. Reference values of anthocyanins were obtained by HPLC-DAD. A number of spectral pretreatments and different mask development strategies were studied. Calibrations were performed by modified partial least-squares regression (MPLS) and present a good potential (RSQ of 0.86 and SEP values of 2.62 and 3.05 mg g(-1) of grape skin for nonacylated and total anthocyanins, respectively) for a fast and reasonably inexpensive screening of these compounds in intact grapes.

A novel method for evaluating flavanols in grape seeds by near infrared hyperspectral imaging.

Chemical composition of seeds changes during grape ripening and this affects the sensory properties of wine. In order to control the features of wines, the condition of seeds is becoming an important factor for deciding the moment of harvesting by winemakers. Sensory analysis is not easy to carry out and chemical analysis needs lengthy procedures, reagents, and it is destructive and time-consuming. In the present work, near infrared hyperspectral imaging has been used to determine flavanols in seeds of red (cv. Tempranillo) and white (cv. Zalema) grapes (Vitis vinifera L.). As reference measurements, the flavanol content was estimated using the p-dimethylaminocinnamaldehyde (DMACA) method. Not only total flavanol content was evaluated but also the quantity of flavanols that would be extracted into the wine during winemaking. A like-wine model solution was used for this purpose. Calibrations were performed by partial least squares regression and they provide coefficients of determination R(2)=0.73 for total flavanol content and R(2)=0.85 for predicting flavanols extracted with model solution. Values up to R(2)=0.88 were reached when cultivars were considered individually.

Impact of adding white pomace to red grapes on the phenolic composition and color stability of Syrah wines from a warm climate.

The influence of the fermentative addition of Pedro Ximenez grape pomace (PXGP, white variety) on the phenolic composition and color of Syrah red wines from a warm climate was studied. Changes on phenolic composition (HPLC), copigmentation/polymerization (spectrophotometry), and color (tristimulus colorimetry) allowed differences among the maceration treatments to be established. PXGP additions at the rates studied increased the extraction of total phenolics, phenolic acids, and monomeric flavanols. However, the effect on the anthocyanins, copigmentation, and polymerization depended on the doses applied, with important consequences on the color. PXGP addition at 10% led to wines with higher polymerization, more stable colors, and bluish hues. in contrast, perceptibly lighter and less intense wines were obtained with PXGP addition at 20%. Thus, the use of white grape byproducts as wine additives at appropriate levels (10% w/w) could improve the phenolic potential of red young wines from a warm climate, contributing to preserve their color characteristic.

Use of near infrared hyperspectral tools for the screening of extractable polyphenols in red grape skins

Hyperspectral images of intact grapes were recorded at harvest time using a near infrared hyperspectral imaging system (900-1700 nm). Spectral data have been correlated with red grape skin extractable polyphenols (total phenolic, anthocyanins and flavanols) by modified partial least squares regression (MPLS) using a number of spectral pretreatments. The obtained results (coefficient of determination (RSQ) and standard error of prediction (SEP), respectively) for the developed models were: 0.82 and 0.92 mg g(-1) of grape skin for extractable total phenolic content, 0.79 and 0.63 mg g(-1) of grape skin for extractable anthocyanin content, 0.82 and 0.45 mg g(-1) of grape skin for extractable flavanol content. The obtained results present a good potential for a fast and reasonably inexpensive screening of the extractable polyphenolic compounds in intact grapes. Moreover, the heterogeneity of extractable polyphenols within the ripeness stage has been also evaluated using the proposed method.

Application of the differential colorimetry and polyphenolic profile to the evaluation of the chromatic quality of Tempranillo red wines elaborated in warm climate. Influence of the presence of oak wood chips during fermentation

The effect of adding American oak wood chips during fermentation on Tempranillo red wines elaborates in a warm climate has been studied. Our attention was focused on the tristimulus colorimetry, differential colorimetry and phenolic compounds related to wine colour. This technique was applied as an oenological alternative to the conventional winemaking for avoiding the common fall of colour of red wines elaborated in warm climates. The addition of oak wood chips promoted the colour enhancement and stabilisation, producing wines with a notably darker colour and with more bluish tonality. This fact was also related to the significantly higher content of some phenolic compounds. On the basis of the results, it could be affirmed that the addition of oak wood chips during fermentation induced visually perceptible colour changes (by the analysis of ΔEab(*), %Δ(2)L, %Δ(2)C and %Δ(2)H), mainly in a quantitative way, and also a lower percentage of diminution of colour.

Application of Differential Colorimetry To Evaluate Anthocyanin–Flavonol–Flavanol Ternary Copigmentation Interactions in Model Solutions

The combined effect of anthocyanin-flavanol-flavonol ternary interactions on the colorimetric and chemical stability of malvidin-3-glucoside has been studied. Model solutions with fixed malvidin-3-glucoside/(+)-catechin ratio (MC) and variable quercetin-3-β-d-glucoside concentration (MC+Q) and solutions with fixed malvidin-3-glucoside/quercetin-3-β-d-glucoside ratio (MQ) and variable (+)-catechin concentration (MQ+C) were tested at levels closer to those existing in wines. Color variations during storage were evaluated by differential colorimetry. Changes in the anthocyanin concentration were monitored by HPLC-DAD. CIELAB color-difference formulas were demonstrated to be of practical interest to assess the stronger and more stable interaction of quercetin-3-β-d-glucoside with MC binary mixture than (+)-catechin with MQ mixture. The results imply that MC+Q ternary solutions kept their intensity and bluish tonalities for a longer time in comparison to MQ+C solutions. The stability of malvidin-3-glucoside improves when the concentration of quercetin-3-β-d-glucoside increases in MC+Q mixtures, whereas the addition of (+)-catechin in MQ+C mixtures resulted in an opposite effect.

Preliminary study to determine the phenolic maturity stage of grape seeds by computer vision.

The applications of computer vision technology for acquiring and analysing images have been extended to the quality evaluation in food industry. This technique involves great advantages for the objective, rapid, non-contact and automated quality inspection and control. The aim of this work was to evaluate the potential of the computer vision to determine the phenolic maturity stage of grape seeds. Up to 21 phenolic compounds were determined by HPLC-DAD-MS in order to obtain reference values to develop the model. The CIELAB parameters, area, aspect, roundness, length, width and heterogeneity of seeds were analysed using a DigiEye(®) system. The technique reported in this work can be a good and rapid tool for taking decisions at harvest time. Notwithstanding, a comprehensive study should be made in order to develop more robust models.

Comparative study on the use of anthocyanin profile, color image analysis and near-infrared hyperspectral imaging as tools to discriminate between four autochthonous red grape cultivars from La Rioja (Spain)

Three independent methodologies were investigated to achieve the differentiation of red grapes from different grape varieties (Garnacha, Graciano, Mazuelo and Tempranillo) collected from five vineyards located in the D.O.Ca. Rioja. Anthocyanin chromatographic analysis, color image analysis and near infrared hyperspectral imaging were carried out for the grapes. Then, a Stepwise Linear Discriminant Analysis (SLDA) was developed for each data set in order to discriminate grapes according to their grape variety. As a result, using anthocyanin profile, color image analysis and near infrared hyperspectral imaging respectively, 88%, 54% and 100% of the samples were correctly classified in the internal validation process and 86%, 52% and 86% were correctly classified in the leave-one-out cross-validation process.