Julio Nogales-Bueno

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.

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.

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.

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.

Screening of anthocyanins in single red grapes using a non-destructive method based on the near infrared hyperspectral technology and chemometrics

BACKGROUND Anthocyanins are the main compounds responsible for the colour of red wines and therefore it may be important to evaluate the content of the aforesaid secondary metabolites during grape ripening due to the crucial importance to determine wine colour. Nowadays, there is a growing demand of rapid and non-destructive analytical tools for analysing grapes, such as the emerging hyperspectral analysis. RESULTS The hyperspectral images of intact grapes (Vitis vinifera L. cv. Tempranillo, Graciano, Garnacha and Mazuelo red grape from vineyards located in the D.O.Ca. Rioja at two different developmental stages) were recorded using a near infrared hyperspectral imaging device (900-1700 nm). Reference values of anthocyanins were obtained by HPLC-DAD. Calibrations were performed by modified partial least squares regression and present a good potential (coefficient of determination of 0.72 and standard error of cross-validation values of 0.78 and 0.70 mg per grape for total and non-acylated anthocyanins respectively). CONCLUSION The procedure reported here presents a good potential for a fast and reasonably inexpensive screening of these compounds in intact single berries. Moreover, the heterogeneity of anthocyanins within the same ripeness stage could be evaluated using this non-detructive tool.

Evaluation of the influence of white grape seed extracts as copigment sources on the anthocyanin extraction from grape skins previously classified by near infrared hyperspectral tools

Hyperspectral imaging has been used to classify red grapes (Vitis vinifera L.) according to their predicted extractable total anthocyanin content (i.e. extractable total anthocyanin content determined by a hyperspectral method). Low, medium and high levels of predicted extractable total anthocyanin content were established. Then, grape skins were split into three parts and each part was macerated into a different model wine solution for a three-day period. Wine model solutions were made up with different concentration of copigments coming from white grape seeds. Aqueous supernatants were analyzed by HPLC-DAD and extractable anthocyanin contents were obtained. Principal component analyses and analyses of variance were carried out with the aim of studying trends related to the extractable anthocyanin contents. Significant differences were found among grapes with different levels of predicted extractable anthocyanin contents. Moreover, no significant differences were found on the extractable anthocyanin contents using different copigment concentrations in grape skin macerations.

Study of phenolic extractability in grape seeds by means of ATR-FTIR and Raman spectroscopy

Near infrared hyperspectral imaging has been applied to grape seeds in order to select a representative subset of samples according to their spectral features in the 900-1700nm range. Afterwards, selected grape seeds have been classified according to their total phenol and flavanol extractabilities. In this way, samples were sorted in three different groups identified as low, medium and high extractability levels. In order to establish the chemical structures which can be responsible for the different extractabilities, vibrational spectroscopy has been applied to the non-extracted material after seed extractions. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Raman spectra of non-extracted seed material have been recorded and their main spectral features have been linked to extractabilities of flavanolic and total phenolic compounds. The vibrational spectroscopic analysis confirms that grape seed phenolic extractability is influenced by the cell wall composition (polysaccharides, lignins, pectins) and by the degree of esterification of pectins.

Simplified method for the screening of technological maturity of red grape and total phenolic compounds of red grape skin: application of the characteristic vector method to near-infrared spectra.

Characteristic vector analysis has been applied to near-infrared spectra to extract the main spectral information from hyperspectral images. For this purpose, 3, 6, 9, and 12 characteristic vectors have been used to reconstruct the spectra, and root-mean-square errors (RMSEs) have been calculated to measure the differences between characteristic vector reconstructed spectra (CVRS) and hyperspectral imaging spectra (HIS). RMSE values obtained were 0.0049, 0.0018, 0.0012, and 0.0012 [log(1/R) units] for spectra allocated into the validation set, for 3, 6, 9, and 12 characteristic vectors, respectively. After that, calibration models have been developed and validated using the different groups of CVRS to predict skin total phenolic concentration, sugar concentration, titratable acidity, and pH by modified partial least-squares (MPLS) regression. The obtained results have been compared to those previously obtained from HIS. The models developed from the CVRS reconstructed from 12 characteristic vectors present similar values of coefficients of determination (RSQ) and standard errors of prediction (SEP) than the models developed from HIS. RSQ and SEP were 0.84 and 1.13 mg g(-1) of skin grape (expressed as gallic acid equivalents), 0.93 and 2.26 °Brix, 0.97 and 3.87 g L(-1) (expressed as tartaric acid equivalents), and 0.91 and 0.14 for skin total phenolic concentration, sugar concentration, titratable acidity, and pH, respectively, for the models developed from the CVRS reconstructed from 12 characteristic vectors.

Linking ATR-FTIR and Raman Features to Phenolic Extractability and Other Attributes in Grape Skin

The importance of wine phenolics on the sensory characteristic of red wines is well-known. Therefore, it is necessary to control the extractability of phenolic compounds from grape skins, which depends significantly on grape ripeness and hence, on cell wall degradation. In the present study, attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Raman spectra of grape skin have been recorded. Then, these spectral matrices have been studied and the main spectral features have been linked to extractabilities of phenolic compounds (anthocyanins, flavanols and total phenols). Moreover, spectral differences between external and internal grape skin surfaces also have been studied. It has been confirmed that the amount of polysaccharides and the degree of esterification of pectins have significant influence on the phenolic extractability levels of grape skin tissue.