Papers by Francisco J. Heredia
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Foods
The usefulness of digital image analysis in estimating sensory attributes of grape seeds in relat... more The usefulness of digital image analysis in estimating sensory attributes of grape seeds in relation to maturation level was evaluated for the first time. Seeds from Syrah grapes harvested throughout the ripening period were grouped according to maturity using the DigiEye® system. The discriminant ability, homogeneity, repeatability, and uniformity of a sensory panel were assessed after training on grape seeds. The aim was to evaluate the use of digital image techniques in order to accurately establish the maturity level of grape seeds, based on sensory and textural features. All sensory attributes (color, hardness, cracking, vegetal, bitterness and astringency) showed significant (p < 0.05) correlations with the chemical maturity stage. Color and vegetal (sensory attributes), together with deformation energy (instrumental texture parameter) (De), allowed for the classification of the seeds into four real maturity stages, hence their usefulness as grape seed ripening indicators. ...
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Foods
Wine color and limpidity are important aspects of consumer preferences. The alteration of these p... more Wine color and limpidity are important aspects of consumer preferences. The alteration of these parameters can damage wine’s appearance but also its mouthfeel characteristics due to its relationship with attributes such as bitterness and astringency. Fining is a practice usually used in enology to modulate undesirable wine organoleptic attributes. However, there are several factors that influence this technique. In this study, the influence of wine pH and ethanol content on grape seed protein fining efficacy has been assessed. Wine clarification, total phenolic and flavanol contents, antioxidant activity, and chromatic parameters have been investigated before and after fining process. The most noticeable clarifying effects were observed for the experimental wines with a lower pH and ethanol content. Control of these factors will make it possible to modulate the main organoleptic properties of the wine, also avoiding the addition of large amounts of fining agents and thus providing g...
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Food Chemistry, 2021
The grape pomace industry produces large quantities of protein-rich seeds, which can be a sustain... more The grape pomace industry produces large quantities of protein-rich seeds, which can be a sustainable nonanimal protein source; their techno-functional properties could be exploited to improve the colour stabilisation and modulating the astringency of red wines in warm climates. This study aims to optimise the methodology of obtaining protein hydrolysates from defatted grape seed meal residue. Five assays using different quantities of enzyme and raw materials were considered. Based on the protein purity, hydrolysates yield, colour and molecular weight distribution achieved, optimal conditions were the hydrolysis of the alkaline protein concentrate with the highest amount of enzyme. The products obtained showed the lowest colour parameters, with the lightness contributing the most to the colour differences, which were visually perceptible (ΔE* ab > 3). The hydrophobic amino acids remained within the peptide sequence, leaving polar and charged amino acids in terminal positions, which could affect the wine equilibrium related to colour stabilisation.
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Molecules, 2020
The influence of post fermentative addition of American barrel-shoot wastes on phenolic compositi... more The influence of post fermentative addition of American barrel-shoot wastes on phenolic composition and chromatic quality of Syrah red wines has been evaluated as an environmentally sustainable alternative to the conventional winemaking for avoiding the common color loss of red wines elaborated in warm climates. American oak wood byproducts added were previously classified by hyperspectral image analysis according to the amount of phenolic compounds transferred to the extraction media. After that, wines were elaborated under different maceration conditions by applying only one proportion of wood (12 g L−1) and two different maceration procedures (simple and double addition) and were compared with a traditionally macerated Syrah red wine (CW, no wood addition). Results proved the effectiveness of the moderate postfermentative addition of oak wood byproducts to stabilize the color of wines and to provoke lower color modification along the time, producing color wines chromatically more...
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Sensors, 2018
Near infrared hyperspectral data were collected for 200 Syrah and Tempranillo grape seed samples.... more Near infrared hyperspectral data were collected for 200 Syrah and Tempranillo grape seed samples. Next, a sample selection was carried out and the phenolic content of these samples was determined. Then, quantitative (modified partial least square regressions) and qualitative (K-means and lineal discriminant analyses) chemometric tools were applied to obtain the best models for predicting the reference parameters. Quantitative models developed for the prediction of total phenolic and flavanolic contents have been successfully developed with standard errors of prediction (SEP) in external validation similar to those previously reported. For these parameters, SEPs were respectively, 11.23 mg g−1 of grape seed, expressed as gallic acid equivalents and 4.85 mg g−1 of grape seed, expressed as catechin equivalents. The application of these models to the whole sample set (selected and non-selected samples) has allowed knowing the distributions of total phenolic and flavanolic contents in th...
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Talanta, Jan 15, 2017
The importance of wine phenolics on the sensory characteristic of red wines is well-known. Theref... more 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.
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Food Chemistry, 2017
Near infrared hyperspectral imaging has been applied to grape seeds in order to select a represen... more 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 900-1700 nm 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.
Molecules, 2016
The influence of adding seeds from grape pomace during Syrah wine fermentation in a warm climate ... more The influence of adding seeds from grape pomace during Syrah wine fermentation in a warm climate has been studied. Seeds of Pedro Ximenez variety were rich in phenolic compounds, mainly flavonoids such as catechin and procyanidins. Changes in total phenolic content (TPC), total flavonoid content (TFC), and antioxidant activity of red wines were observed. These changes depended on the vinification stage and the amount of seeds (SW: 450 g or DW: 900 g seeds/150 kg grapes) applied. In general, antioxidant activity was greater when a simple dose (SW) was considered. Results indicate that seeds rich in flavonoids could be used as wine additives, which could improve the antioxidant potential of red wines in a warm climate.
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Talanta, 2016
Grape seeds were collected in ten different dates and classified in seven groups according to the... more Grape seeds were collected in ten different dates and classified in seven groups according to their individual hyperspectral imaging characteristics. Proanthocyanidin composition was studied using HPLC-MS for oligomers and acid catalyzed cleavage for polymers characterization. The combination of both analysis provided a complete description of the flavanols. Chemometric analysis was performed to summarize the analytical results. None of the considered variables presented statistical differences among all groups. From one to five groups were found for each variable, while three was the most frequent value, consequently three putative stages might be considered the real number of different analytical stages since it is the number of statistically significant groups for the majority of the compounds. This classification could be considered as the first step to optimize the use of seeds in winemaking to minimize the gap between sugar and phenolic maturities, consequence of the global climate change, mainly observed in warm climate.
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Journal of the Science of Food and Agriculture, 2015
BACKGROUNDAnthocyanins are the main compounds responsible for the colour of red wines and therefo... more BACKGROUNDAnthocyanins 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.RESULTSThe 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‐acyla...
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Journal of agricultural and food chemistry, Jan 21, 2015
Characteristic vector analysis has been applied to near infrared spectra to extract the main spec... more 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 (RMSE) 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 in order to predict skin total phenolic concentration, sugar concentration, titratable acidity and pH by modified partial least squares regression (MPLS). The obtained results have been compared with those previously obtained from HIS. The models developed from the CVRS reconstructed from 12 ch...
Talanta, 2015
Three independent methodologies were investigated to achieve the differentiation of red grapes fr... more 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.
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Food Chemistry, 2015
Hyperspectral images of intact grapes were recorded at harvest time using a near infrared hypersp... more 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 À1 of grape skin for extractable total phenolic content, 0.79 and 0.63 mg g À1 of grape skin for extractable anthocyanin content, 0.82 and 0.45 mg g À1 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.
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Food Research International, 2014
The potential use of ulluco (Ullucus tuberosus) extracts to be added as natural colorant to other... more The potential use of ulluco (Ullucus tuberosus) extracts to be added as natural colorant to other products has been studied. The stability of ulluco extracts at different pHs and temperatures over time has been thoroughly conducted. Our attention was focused on the tristimulus colorimetry, differential colorimetry and betalains related to color. On the basis of the results, although ulluco extract adjusted to pH 4 showed a significantly lower color intensity (C* ab ~40), the stability of red hue (h ab ) over time was higher. Betalain content showed the same trend, and lower values in highly-acidic extracts have been reported. It could be also affirmed that visually appreciable color changes (ΔE* ab N 2) were induced when pH changed and different temperatures were applied. Despite of the vivid red color of the initial extracts, ulluco extracts added to low-acidic foodstuffs showed a tendency towards yellowish tonalities (values of h ab from 45°to 80°), mitigated by using refrigeration storage conditions (h ab values from 45°to 55°).
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Journal of Agricultural and Food Chemistry, 2001
A pigment derived from the acetaldehyde-mediated condensation between (+)-catechin and malvidin 3... more A pigment derived from the acetaldehyde-mediated condensation between (+)-catechin and malvidin 3-O-glucoside has been prepared and isolated by semipreparative HPLC, and its characteristics of color and stability have been studied and compared with that of malvidin glucoside in aqueous solutions. When the pH was increased from 2.2 to 5.5, the solution of the pigment became progressively more violet (λ max ) 560 nm at pH 5.5), whereas similar solutions of the anthocyanin were almost colorless at pH 4.0. This behavior indicated that the anthocyanin moiety of the pigment was more protected against water attack, and thus the formation of its quinonoidal forms was favored. The color of the pigment also showed more stability with regard to bleaching by SO 2 than that of malvidin glucoside. Nevertheless, the pigment was more sensitive to degradation in aqueous solution than the anthocyanin. The cleavage of the ethyl bridge that links the anthocyanin and the catechin constituted the first step in its degradation, as demonstrated by the formation of malvidin glucoside as a major product.
Journal of Agricultural and Food Chemistry, 2006
International Journal of Food Properties, 2013
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Food Research International, 2013
The aim of this work was to conduct a detailed colorimetric study, using transmittance and reflec... more The aim of this work was to conduct a detailed colorimetric study, using transmittance and reflectance measurements, to evaluate the possible interactions occurring among the different families of pigments comprising to colour matter of red wines and their contribution to the colour in aged red wines. To accomplish this, the phenolic material of monovarietal red wines obtained from Tempranillo and Graciano varieties, and their blends, were fractionated by gel permeation chromatography in order to separate the coloured fractions with different chemical compositions. The binary blends at different concentrations of the fractions having higher anthocyanin monoglucoside proportions with fractions having higher pyranoanthocyanin derivative contents and direct flavanol-anthocyanin condensation products were carried out in order to determine the effect of adding these derivatives on the colour of the anthocyanin monoglucosides, the major wine pigments. It was observed that the addition of derived pigments to the anthocyanin monoglucosides fraction resulted in colour differences perceptible by the human eye. These variations were mainly quantitative (changes in chroma and lightness), and were also qualitative (changes in hue) in monovarietal wines. Studying the phenolic fractions of wines implies an approach to the chemical reality of the wines, more than the studies on model solutions, since they can lead to the knowledge of those components having more influence on the final colour of the wine. With these results the wineries could conduct the vinifications towards a higher extraction of the components or families of components more important for the intensity and stability of colour.

Analytica Chimica Acta, 2012
The aim of the present work was to determine whether there is any relationship between measuremen... more The aim of the present work was to determine whether there is any relationship between measurement by transmission and reflection (in the latter case, with and without contact with the sample). We also evaluated which methodology used would offer a better interpretation of the results in visual terms. For this purpose, different colorimetric techniques such as transmission spectrophotometry, diffuse reflectance spectrophotometry and spectroradiometry were applied. The samples consisted of increasing dilutions (0, 20, 40, 60, 80 and 100%) of the phenolic fractions obtained from 4 wines: Tempranillo (T) and Graciano (G) monovarietal wines, and two 80:20 mixtures: M (wine elaborated by blending grapes) and W (a blend of the T and G wines) (9 fractions per wine). Fractionation was performed using gel permeation chromatography with a Toyopearl HW-40S column, and the dilutions of the fractions were performed with synthetic wine (pH = 3.6). The spectroradiometric measurements permitted the differences due to the dilution effect on the fractions to be established more clearly than with the results obtained using diffuse reflectance and spectrophotometry. Thus, this technology is very suitable for use in comparative interpretations by the human eye. In turn, we assessed the changes in colour due to the effect of dilution on the fractions, observing that the effect of dilution led to an increase in the values of lightness (L*), while the chroma values (C* ab ) followed the opposite trend, in agreement with its role as a variable related to chromatic intensity or vividness of the sample. In contrast, hue (h ab ) did not seem to be affected by dilution of the fractions, in consonance with the qualitative nature of this parameter.
Analytica Chimica Acta, 2012
The applications of computer vision technology for acquiring and analysing images have been exten... more 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.
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Papers by Francisco J. Heredia