Influence of Temperature during Pre-Fermentative Maceration and Alcoholic Fermentation on the Phenolic Composition of 'Cabernet Sauvignon' Wines.

This study presents the effects of different working temperatures on the transfer of compounds during the pre-fermentative and fermentative stages of the wine making process with 'Cabernet Sauvignon' grapes. Two different procedures have been evaluated. Firstly, the pre-fermentative maceration of the crushed grapes at two different temperatures (20 °C and 10 °C). Then, the alcoholic fermentation under two different sets of conditions, the fermentation at a constant temperature of 20 °C and the fermentation under a positive temperature gradient from 10 to 20 °C. According to the experimental results, the phenolic contents (total phenolics, total anthocyanins, and total tannins) were mainly conditioned by the fermentation temperature, however the pre-fermentative conditions also affected the content levels of these compounds. Furthermore, the use of a fermentation temperature gradient improved the organoleptic characteristics of the wines. However, the color was not as stable as that of wines produced through fermentation at a higher constant temperature. Consequently, the implementation of a temperature gradient during the alcoholic fermentation process is recommended and a longer period at high temperature over the last phase of the process would be desirable to obtain aromatic wines with the desirable color stability.

Application of accelerating energies to the maceration of sherry vinegar with citrus fruits.

BACKGROUND: In the present work we propose the use of accelerating energies (microwaves and ultrasounds) to the maceration process of sherry vinegar with citrus fruit peels (orange and lemon). For the application of microwaves, an experimental design has been developed in order to optimize the maceration conditions. To evaluate the effect of these energies on the maceration, the volatile and polyphenolic content of the samples has been analyzed, as well as their sensory characteristics. RESULTS: Orange peel provided a higher number of volatile and polyphenolic compounds to the vinegar, while lemon's yielded a greater amount of some of them. The multivariate analysis showed that the samples macerated using microwaves were the most similar to the samples macerated in the traditional way. This aspect was corroborated by the sensory analysis, which was more noticeable when orange peel was used in the macerations. CONCLUSION: Therefore, it seems that the use of microwaves to accelerate maceration is a good alternative to the traditional method of making sherry vinegars macerated with citrus peel, since it cuts down the maceration time from 3 days to just a few minutes. © 2020 Society of Chemical Industry.

Influence of Two Different Cryoextraction Procedures on the Quality of Wine Produced from Muscat Grapes.

Freezing grapes is a winemaking technique known as cryoextraction that intends to modify the composition of the final wines. The changes that take place in the frozen grapes facilitate the transfer of certain compounds from the grape skins into the musts because of the grape's unstructured tissues. For this study, the white grape variety Muscat of Alexandria was selected. Two different cryoextraction procedures have been analyzed as follows: (i) Ultrafast freezing, and (ii) liquid nitrogen freezing. The wines obtained using liquid nitrogen freezing exhibited higher levels of terpenoids, as well as higher levels of hydroxylic compounds and fatty acids than both the wines obtained through traditional methods and ultrafast freezing wines. In any case, both freezing techniques produced wines of a more intense aroma compared with those wines obtained by traditional methods. In fact, liquid nitrogen freezing produced the wines with the most intense aroma and were the best valued by the tasting panel.

Use of ultrasound at a pilot scale to accelerate the ageing of sherry vinegar.

In the present work, the accelerated ageing process of sherry vinegar has been studied at pilot scale by means of the joint application of ultrasound, micro-oxygenation and wood chips (American oak, French oak and Spanish oak). The CIELab parameters have been studied as well as the polyphenolic and volatile content of the aged vinegar samples. Vinegars aged with American oak presented different chromatic characteristics to those aged with French and Spanish oak and a lower polyphenolic and volatile content than the latter ones. On the other hand, Spanish oak generated vinegars with a higher content of volatile compounds and an intermediate polyphenolic profile between those obtained using French and American oak. In addition, the use of ultrasound for a period between 4 and 21 days, generated vinegars with similar characteristics to others that were aged in the traditional way for between 2 and 6 months. It has been demonstrated that the use of ultrasound, combined with micro-oxygenation and chip addition, is a technique which can accelerate the ageing process of vinegars at a pilot scale, so it could be a viable alternative to obtain sherry vinegars aged in a shorter time.

Use of Sensory Analysis to Investigate the Influence of Climate Chambers and Other Process Variables in the Production of Sweet Wines.

In this study, a climate chamber, as an alternative method, has been used to dry raisins and the sensory profiles of the sweet sherry wines obtained have been evaluated. Other important factors, namely grape variety, vintage, vinification conditions, as well as the ageing method and its length of time, have also been considered. When heavy rainfall had been registered, the musts extracted from grapes dried under controlled conditions in a climate chamber showed a lower intensity of the musty off-odor compared to those elaborated with sun-dried grapes. The wine fermented at low temperature with Saccharomyces bayanus scored the highest in citric and floral notes, and this was preferred over all the other wines that were evaluated. The wines aged in oak barrels were preferred to both, wines aged in the presence of oak chips as well as those aged without any wood contact. The use of climate chambers to dry the grapes that are going to be used for the elaboration of sweet wines appears to be an advantageous alternative to the traditional method, since it allows a more precise control of the process and highly valued sweet wines from a sensory point of view are obtained thereby.

Development of Head Space Sorptive Extraction Method for the Determination of Volatile Compounds in Beer and Comparison with Stir Bar Sorptive Extraction.

A headspace sorptive extraction method coupled with gas chromatography-mass spectrometry (HSSE-GC-MS) was developed for the determination of 37 volatile compounds in beer. After optimization of the extraction conditions, the best conditions for the analysis were stirring at 1000 rpm for 180 min, using an 8-mL sample with 25% NaCl. The analytical method provided excellent linearity values (R2 > 0.99) for the calibration of all the compounds studied, with the detection and quantification limits obtained being low enough for the determination of the compounds in the beers studied. When studying the repeatability of the method, it proved to be quite accurate, since RSD% values lower than 20% were obtained for all the compounds. On the other hand, the recovery study was successfully concluded, resulting in acceptable values for most of the compounds (80%-120%). The optimised method was successfully applied to real beer samples of different types (ale, lager, stout and wheat). Finally, an analytical comparison of the optimised HSSE method, with a previously developed and validated stir bar sorptive extraction (SBSE) method was performed, obtaining similar concentration values by both methods for most compounds.

Suitability of alternative wood types other than American oak wood for the ageing of Sherry vinegar.

The present study has consisted on the monitoring of Sherry vinegar during a whole year ageing in American oak, French oak, Spanish oak and chestnut barrels in order to determine the suitability of alternative wood types other than American oak for the ageing of this type of vinegar. Thirty-two volatile compounds were quantified, CIELab parameters were determined and sensory analyses were carried out during the whole process. The multivariate analysis of the data revealed that the samples that had been aged in Spanish oak barrels were getting more similar to those aged in French oak as the ageing process was progressing. Furthermore, the samples that had been aged in chestnut presented some volatile compounds significantly different from American oak. Finally, although French oak wood transferred the best organoleptic characteristics to Sherry vinegar, Spanish oak and chestnut seemed to be satisfactory alternatives for the ageing process.

Effect of the type of wood used for ageing on the volatile composition of Pedro Ximénez sweet wine.

BACKGROUND: The present study investigated the volatile composition of a Pedro Ximénez sweet wine that had been aged in barrels made of different types of wood (Spanish oak, French oak, American oak and chestnut) and subjected to different degrees of toasting (medium toasting and intense toasting). The analyses were carried out using stir bar sorptive extraction gas chromatography-mass spectrometry after validation of the matrix in this case. RESULTS: Good values of linearity, precision, limits of detection and limits of quantification were obtained for the 36 compounds studied, six of which were identified for the first time in Pedro Ximénez (propyl acetate, cis-3-hexenyl acetate, benzyl acetate, guaiacol, trans-whiskeylactone and 4-ethylguaiacol). The volatile composition of the samples varied as the ageing process progressed, and higher volatile concentrations were obtained in samples aged in barrels that had been intensely toasted compared to in those with medium toasting. A multivariate statistical study allowed the samples to be correctly classified according to ageing time, wood toasting and the type of wood used for ageing. CONCLUSION: The organoleptic analysis performed on the Pedro Ximénez sweet wine samples resulted in differences between the wines aged in the different types of wood during the early weeks of ageing, and scarce differences towards the end of the study period. At the end of the process, all of the wines were better valued and wines aged in medium toasted barrels were the best rated by the panel of judges for all four woods under investigation. This fact could indicate the suitability of alternative woods for the ageing of Pedro Ximénez sweet wines. © 2020 Society of Chemical Industry.

Development of a stir bar sorptive extraction method to study different beer styles volatile profiles.

A stir bar sorptive extraction method coupled to Gas Chromatography-Mass Spectrometry for the analysis of 52 volatile compounds in beer has been developed. The final optimized conditions were: 50 mL sample volume, 180 min extraction time, 25% (w/v) NaCl content and polydimethylsyloxane stir bars. Good values of linearity (R2 > 0.99) were achieved for the calibration lines of all the compounds. The limits of detection and quantification obtained were low enough for the determination of the volatile compounds in the samples and the recovery values obtained for the majority of the compounds were between 80% and 120%. The precision of the method was also studied and acceptable values for this type of extraction technique were obtained (<20%). 30 samples of different styles of beers (ale, lager, stout and wheat) were analysed and their aromatic profile was characterised. Multivariate statistical techniques allowed the correct classification of the samples according to their volatile composition.

Characterization and Differentiation of Spanish Vinegars from Jerez and Condado de Huelva Protected Designations of Origin.

Thirty one Jerez vinegar samples and 33 Huelva vinegar samples were analyzed for polyphenolic and volatile compound content in order to characterize them and attempt to differentiate them. Sixteen polyphenolic compounds were quantified by means of ultraperformance liquid chromatography method with diode array detection (UPLC-DAD), and 37 volatile compounds were studied by means of stir bar sorptive extraction-gas chromatography-mass spectrometry (SBSE-GC-MS). Spectrophotometric CIELab parameters were also measured for all the samples. The results obtained from the statistical multivariate treatment of the data evidenced a clear difference between vinegars from the two geographical indications with regard to their polyphenolic content, with Jerez vinegars exhibiting a greater phenolic content. Differentiation by the volatile compound content was, however, not so evident. Nevertheless, a considerable differentiation between the two groups of vinegars based on their volatile fraction was achieved. This may bring to light the grape varieties and geographical factors that have a clear influence on such differences.

FT-IR, Vis spectroscopy, color and multivariate analysis for the control of ageing processes in distinctive Spanish wines.

During the ageing period, diverse physicochemical changes occur affecting the quality of the final product. For this reason, it is important to study and optimize this step. Fourier transform infrared (FT-IR) and UV-visible (UV-Vis) spectroscopic techniques combined with multivariate analysis were used to obtain regression models to correlate both spectroscopic data and chromatic parameters with the ageing level of high quality Sherry wines. Three spectral ranges were obtained that contain the highest variance: two different fingerprint ranges in FT-IR (1100-2000 cm-1 and 2300-2999 cm-1) and one range in the visible region (380-450 nm). The regression model has enabled full differentiation between the seven levels of ageing in the wine explored. A good linear regression fit (R2 above 0.95) was obtained regardless of the ranges used. The results demonstrate that both spectroscopic techniques can be used to optimize the ageing process in a simple and fast way.

Rapid quantification of honey adulteration by visible-near infrared spectroscopy combined with chemometrics.

Honey is a pure product for which the addition of any other substance is prohibited by international regulations. Therefore, it is necessary to develop reliable analytical methods to guarantee its authenticity. Visible-near infrared spectroscopy (Vis-NIRS) combined with chemometric tools, like hierarchical cluster analysis (HCA), principal component analysis (PCA), linear discriminant analysis (LDA), has been used for the discrimination of honey adulterated with high fructose corn syrup (HFCS). Different honey samples from the Granada Protected Designation of Origin (Spain) were adulterated with HFCS at different percentages (10 - 90%). LDA was able to discriminate 100% of the samples. Partial least squares regression (PLS) was used to predict the level of adulteration. The best prediction model used 10 factors with a high coefficient of determination near 1. The developed method showed high precision (coefficient of variation below 4%). Vis-NIRS combined with chemometrics can be used for the rapid and non-destructive detection of honey adulteration. The obtained results demonstrate that the application of this technique as a screening method could be a useful tool for quality monitoring analysis in routine laboratories.

An Electronic Nose Based Method for the Discrimination of Weathered Petroleum-Derived Products.

In recent years pollution due to hydrocarbon spills has increased markedly as a result of the numerous advances in technologies and industrial processes. Anthropogenic activities (accidental or illegal) are responsible for most of these incidents. In some cases, the spills are not detected at the moment they occur and the contaminants are subjected to different degradation phenomena that may change the chemical composition of the hydrocarbon over time. An incorrect or ineffective identification of the spill could lead to significant consequences, bearing in mind that most spills are hazardous to the environment. In the present work the capacity of the analytical technique based on the Electronic Nose (eNose) combined with chemometrics in the identification and discrimination of different weathered petroleum-derived products (PDPs) was studied. Different volumes (40 μL and 80 μL) of PDPs (gasoline, diesel, and paraffin) were poured onto different supports (wood, cork, paper, and cotton sheet) and subjected to a natural weathering process by evaporation for one month. The porosity of the support was also studied. The application of linear discriminant analysis allowed the full discrimination of the samples according to the presence/absence of PDP and a 97.7% of correct discrimination of the different PDPs regardless of the weathering time, support or volume used. The results show that the system is capable of detecting and discriminating the presence of petroleum-derived products in any of the situations studied.

Optimization of a multiple headspace sorptive extraction method coupled to gas chromatography-mass spectrometry for the determination of volatile compounds in macroalgae.

A novel extraction technique is proposed in which the Multiple Headspace Extraction (MHE) approach is used in conjunction with Headspace Sorptive Extraction (HSSE) and Gas Chromatography-Mass Spectrometry (GC-MS) detection. The extraction method was developed to determine volatile compounds in macroalgae. Optimization of the extraction parameters was carried out using design of experiments to identify factors that affect the extraction: extraction time, temperature, twister length and amount of sample. The results of the optimization led to an extraction of 2 g of sample using a 20 mm Twister® at 66 °C for 180 min. The progression constants (ß) were calculated for 43 volatile compounds, 29 of which could be quantified using the method. Linearity was attained with a determination coefficient higher than 0.99 for all studied compounds. Inter-day and inter-twister precisions ranged from 0.22% to 19.01% and from 0.69% to 14.76% respectively, and values below 10% were obtained for the majority of compounds. LOD and LOQ values ranged from the values obtained for diethyl succinate (0.012 µg/L and 0.088 µg/L, respectively) and those obtained for dimethyl sulfide (5.544 µg/L and 40.286 µg/L, respectively). However, for the majority of compounds values obtained were below 1 µg/L (LOD) and 5 µg/L (LOQ). Compounds such as ethyl acetate, hexanal, heptadecane, 2-hexenal, 6-methyl-5-hepten-2-one, dimethyl sulfide, benzyl alcohol, beta ionone, or beta cyclocitral, among others were correctly determined in three species of macroalgae: Ulva sp., Gracillaria sp. and Enteromorpha sp.

Study of the Weathering Process of Gasoline by eNose.

In a fire investigation the rapid detection of the presence of ignitable liquids like gasoline is of great importance as it allows appropriate treatment of the remains, the identification of prevention methods and detects the possible presence of an arsonist. In some cases, analysts cannot access the fire scene in the first few hours due to the dangers involved in the situation and, as a consequence, phenomena such as weathering start. Ignitable liquid weathering is an evaporation process that results in an increase in the abundance of non-volatile compounds relative to volatile compounds, and this process changes the chemical composition. In the present work, the weathering of samples of gasoline at different times (from 0 h to a month) has been studied using an electronic nose (eNose). The influence of the volume used (40 µL and 80 µL) and the type of support (cork, wood, paper and cotton sheet) has been studied. Chemometric tools have been used with the aim of ascertaining the weathering time for which the developed method is capable of detecting the presence of gasoline. The eNose was able to discriminate samples of weathered gasoline. The support used for the samples did not seem to have an influence on the detection and the system.

Fast analysis of capsaicinoids in Naga Jolokia extracts (Capsicum chinense) by high-performance liquid chromatography using fused core columns.

A rapid high-performance liquid chromatography method with a C18 reverse-phase fused-core column has been developed for the determination and quantification of the main capsaicinoids (nornordihydrocapsaicin, nordihydrocapsaicin, capsaicin, dihydrocapsaicin, homocapsaicin and homodihydrocapsaicin) present in Naga Jolokia peppers. A fused-core Kinetex™ C18 column (50×2.1mm i.d.; 2.6µm) was used for the analysis. The chromatographic separation was obtained with a gradient method in which the mobile phase was water (0.1% acetic acid) as solvent A and acetonitrile (0.1% acetic acid) as solvent B. The separation of all compounds was achieved in less than 3min with a total analysis time (sample-to-sample) of 10min. The robustness of the method was evaluated. The method showed excellent repeatability and intermediate precision expressed as coefficient of variance of less than 2%. The developed method was employed for the quantification of the major capsaicinoids present in different peppers and commercial products containing chilli peppers.

Characterization and Differentiation of Petroleum-Derived Products by E-Nose Fingerprints.

Characterization of petroleum-derived products is an area of continuing importance in environmental science, mainly related to fuel spills. In this study, a non-separative analytical method based on E-Nose (Electronic Nose) is presented as a rapid alternative for the characterization of several different petroleum-derived products including gasoline, diesel, aromatic solvents, and ethanol samples, which were poured onto different surfaces (wood, cork, and cotton). The working conditions about the headspace generation were 145 °C and 10 min. Mass spectroscopic data (45-200 m/z) combined with chemometric tools such as hierarchical cluster analysis (HCA), later principal component analysis (PCA), and finally linear discriminant analysis (LDA) allowed for a full discrimination of the samples. A characteristic fingerprint for each product can be used for discrimination or identification. The E-Nose can be considered as a green technique, and it is rapid and easy to use in routine analysis, thus providing a good alternative to currently used methods.

Tryptophan Levels during Grape Ripening: Effects of Cultural Practices.

Some cultural practices that are carried out during the grape ripening period are associated with vine stress, including leaf removal, grape bunch removal, and vegetable cover crops. Additionally, several nitrogen and sulfur supplements have also been used directly on leaves during the last stage of the ripening period. In the work described here, five different cultural practices and the reference were applied in three replicates in the same vineyard. The evolution of tryptophan levels was evaluated from just after grape veraison until the harvest date. In some cases, certain specific treatments were also evaluated after the regular harvest date. The cultural techniques that involved the application of nitrogen led to higher levels of tryptophan at the harvest day when compared to other cultural techniques. It was also found that the application of nitrogen without sulfur had a faster effect on the level of tryptophan. It was established that a period of around 20 days is needed for the grapes to show clear differences in tryptophan levels after the application of nitrogen.

Ontogenetic Variation of Individual and Total Capsaicinoids in Malagueta Peppers (Capsicum frutescens) during Fruit Maturation.

The ontogenetic variation of total and individual capsaicinoids (nordihydrocapsaicin (n-DHC), capsaicin (C), dihydrocapsaicin (DHC), homocapsaicin (h-C) and homodihydrocapsaicin (h-DHC)) present in Malagueta pepper (Capsicum frutescens) during fruit ripening has been studied. Malagueta peppers were grown in a greenhouse under controlled temperature and humidity conditions. Capsaicinoids were extracted using ultrasound-assisted extraction (UAE) and the extracts were analyzed by ultra-performance liquid chromatography (UHPLC) with fluorescence detection. A significant increase in the total content of capsaicinoids was observed in the early days (between 12 and 33). Between day 33 and 40 there was a slight reduction in the total capsaicinoid content (3.3% decrease). C was the major capsaicinoid, followed by DHC, n-DHC, h-C and h-DHC. By considering the evolution of standardized values of the capsaicinoids it was verified that n-DHC, DHC and h-DHC (dihydrocapsaicin-like capsaicinoids) present a similar behavior pattern, while h-C and C (capsaicin-like capsaicinoids) show different evolution patterns.

Multiresponse optimization of a UPLC method for the simultaneous determination of tryptophan and 15 tryptophan-derived compounds using a Box-Behnken design with a desirability function.

A Box-Behnken design was used in conjunction with multiresponse optimization based on the desirability function to carry out the simultaneous separation of tryptophan and 15 derivatives by Ultra Performance Liquid Chromatography. The gradient composition of the mobile phase and the flow rate were optimized with respect to the resolution of severely overlapping chromatographic peaks and the total run time. Two different stationary phases were evaluated (hybrid silica and a solid-core-based C18 column). The methods were validated and a suitable sensitivity was found for all compounds in the concentration range 1-100µgL-1 (R2>0.999). High levels of repeatability and intermediate precision (CV less than 0.25% and 1.7% on average for the retention time and the signal area, respectively) were obtained. The new method was applied to the determination tryptophan and its derivatives in black pigmented glutinous and non-glutinous rice grain samples.