Discrimination of Port wines by style and age using chromatic characteristics, phenolic, and pigment composition.

The colour of the different Port wine styles and indication of age (IOA) categories is a distinctive quality parameter influenced by the grapes and ageing process. The impact of Port wine styles and IOA on phenolic composition is mostly unknown. This work aims to study the chromatic characteristics (CIELab) and their relation with the phenolic composition of White, Tawny, and Ruby Port wines and evaluate the feasibility of its utilisation for their discrimination. Port wine styles and IOA categories can be discriminated by their chromatic characteristics, using different data analysis models. The higher b* values, corresponding to the brownish/yellowish colour of Tawny and White Ports belonging to higher IOA categories, seem more related to the sugar browning than the oxidative change in phenolic compounds. However, this last process is essential for the red colour (a*) decrease of Tawny Port wines with higher IOA.

Fast and Simple UPLC-Q-TOF MS Method for Determination of Bitter Flavan-3-ols and Oligomeric Proanthocyanidins: Impact of Vegetable Protein Fining Agents on Red Wine Composition.

Wine phenolic compounds, particularly proanthocyanidins (PAs), play a significant role in wine sensory characteristics, specifically bitterness and astringency. Although not consensual, flavan-3-ols and oligomeric PAs are generally considered the primary contributors to wine bitterness. Patatin, a vegetable protein fining agent, has been explored as an alternative to animal and synthetic fining agents for reducing wine bitterness. However, contradictory results exist regarding its effectiveness in removing flavan-3-ols and oligomeric PAs in red wines. In this work, a UPLC-Q-TOF MS/MS method was optimized and validated for accurately measuring flavan-3-ols, as well as dimeric and trimeric PAs, in red wines. The MS/MS analysis of flavan-3-ols, in addition to the typical fragmentation described in the literature, revealed an intense mass fragment resulting from the loss of C3O2 and C3O2 + H2O from the parent ion. It was observed that flavan-3-ols and PAs undergo oxidation during sample preparation, which was reversed by the addition of 5 g/L of ascorbic acid. The method demonstrated good linearity range (2 mg/L to 20 mg/L), detection limit (0.3 mg/L to 0.7 mg/L), quantification limit (0.8 mg/L to 2.2 mg/L), precision (repeatability 2.2% to 7.3%), and accuracy (recovery 98.5% to 100.5%). The application of patatin at different doses (5 g/L to 30 g/L) in two different red wine matrices did not reduce the levels of monomeric, dimeric, and trimeric PAs in red wines. However, similar behaviors were observed for pea protein and gelatin. Therefore, wine fining trials and efficiency measurements of the treatments in each matrix are strongly advised.

Development and validation of a multiple headspace solid-phase microextraction method for accurate and precise analysis of the aroma of Tawny and White Port wines.

An accurate and precise Multiple Headspace Solid-Phase Microextraction (MHS-SPME) method was developed and validated for quantifying the volatile composition of White and Tawny Port wines. SPME extraction conditions were optimised using a four-factor three-level Box-Behnken design with three blocks and two replications. Optimal extraction conditions were similar for both Port wines. The method showed good linearity (0.001-50 mg/L), precision (<5%), and detection limits (<1µg/L), well below the olfactory detection threshold. Recoveries higher than 95 % were obtained. Twenty-three aroma compounds were quantified in Tawny and, for the first time, in White Port wines, including five acids, fourteen esters, the most abundant class, and four norisoprenoids, whose levels apparently increased with age. White Port wines had a lower abundance of aroma compounds. Results show that this MHS-SPME method is suitable for analysing volatile composition of White and Tawny Port wines, with reduced costs, manipulation time and eliminating matrix effects.

Reductive amination of aldehyde 2,4-dinitrophenylhydrazones using cyanoborohydride for determination of selected carbonyl compounds in Port wines, table wines, and wine spirits.

Carbonyl compounds are mainly analysed by HPLC with ultraviolet detection after reaction with DNPH, yielding carbonyl-hydrazones. The presence of geometrical isomers whose relative abundance is dependent on the reaction condition introduces analytical errors and increases the complexity of the chromatograms. In this work, a simple, fast, and robust method for determining pyruvic acid, acetaldehyde, and α-ketobutyric acid in Port wines, dry table wines, and wine spirits by reductive amination of aldehyde 2,4-dinitrophenylhydrazones using cyanoborohydride followed by HPLC-DAD was developed, optimised and validated. The developed method was simple and showed good performance in several parameters such as linearity (0.025-200 mg/L), detection limits (0.0043-0.0097 mg/L), quantification (0.014-0.032 mg/L), precision (1.1-4.2 %) and accuracy (99.02 %). The method was applied to five different wine matrices, White, Tawny, and Ruby Port wines, white and red table wines, and wine spirits. The quantification of these carbonyl compounds simultaneously was achieved in Port wines for the first time.

Air-Depleted and Solvent-Impregnated Cork Powder as a New Natural and Sustainable Fining Agent for Removal of 2,4,6-Trichloroanisole (TCA) from Red Wines.

Trichloroanisole (TCA) in wine results in a sensory defect called "cork taint", a significant problem for the wine industry. Wines can become contaminated by TCA absorption from the atmosphere through contaminated wood barrels, cork stoppers, and wood pallets. Air-depleted solvent-impregnated (ADSI) cork powder (CP) was used to mitigate TCA in wines. The ADSI CP (0.25 g/L) removed 91% of TCA (6 ng/L levels), resulting in an olfactory activity value of 0.14. A Freundlich isotherm described ADSI CP TCA adsorption with irreversible adsorption and a KF = 33.37. ADSI CP application had no significant impact on the phenolic profile and chromatic characteristics of red wine. Using headspace sampling with re-equilibration, an average reduction in the volatile abundance of 29 ± 15%, 31 ± 19%, and 37 ± 24% was observed for the 0.10, 0.25, and 0.50 g/L ADSI CP, respectively. The alkyl esters and acids were the most affected. The impact observed was much lower when using headspace sampling without re-equilibration. Isoamyl acetate, ethyl hexanoate, ethyl hexanoate, and ethyl decanoate abundances were not significantly different from the control wine and 0.25 g/L ADSI CP application. Thus, ADSI CP can be a new sustainable fining agent to remove this "off-flavor" from wine, with a reduced impact on the wine characteristics.

Is pinking susceptibility index a good predictor of white wines pinking phenomena?

The concentration of anthocyanins in white wines from different grape varieties (Prosecco, Sauvignon Blanc, Pinot Grey, Chardonnay, Síria) from diverse countries (Italy, Moldova, and Portugal) was determined. Anthocyanins, mainly malvidin-3-O-glucoside, were detected in all wines (from 0.7 to 704 µg/L). No correlation between anthocyanins concentration and the Pinking Susceptibility Index (PSI) was observed contrarily to the colour of wines exposed to oxygen (r = 0.871, p < 0.00005). The oxidation of wines with hydrogen peroxide resulted in the formation of various compounds. PSI was correlated with compounds absorbing in the 400-480 nm region, probably more related to the browning than the pinking phenomenon. The lack of correlation between the PSI and anthocyanins concentration in white wines can be due to the different chemical compositions of white wines that yield various compounds after oxidation that might not be related to the natural wine pinking phenomenon.

Reducing the Negative Effect on White Wine Chromatic Characteristics Due to the Oxygen Exposure during Transportation by the Deoxygenation Process.

In white wine production, a great effort is made to avoid extensive contact with oxygen, which might adversely affect color and aroma. In this work, the impact of bulk transportation on white wine oxygen uptake and the effect of deoxygenation on white wine dissolved oxygen levels, as well on the phenolic composition and chromatic characteristics of white wines stored for nine months, were studied. Transportation increased the white wine dissolved oxygen content (117 and 181% in the wines studied) that increased the free sulfur dioxide loss during storage. Moreover, deoxygenation of white wines reduced the increase in the yellow color of white wines during storage, probably related to the higher levels of free sulfur dioxide that remain in these wines during storage. Furthermore, the amount of wine phenolics also have a decisive influence on wine color characteristics evolution, with increased levels of total phenolic compounds increasing the variation in the b *(measure of yellowness) values of the wines after nine months of storage. Results show the negative impact of bulk transportation on white wine color characteristics; however, wine deoxygenation is a good practice to minimize those aspects, preserving color characteristics.

Efficiency of carboxymethylcellulose in red wine tartaric stability: Effect on wine phenolic composition, chromatic characteristics and colouring matter stability.

In this work, the effect of carboxymethylcellulose structural features on the efficiency to prevent potassium hydrogen tartrate precipitation in red wines and on the phenolic composition, chromatic characteristics and colouring matter stability was studied. The degree of substitution of carboxymethylcellulose was important for its efficiency in highly unstable wines. Application of carboxymethylcellulose doesn't result in a significant change in the phenolic, monomeric anthocyanin composition, colour intensity, and chromatic characteristics of red wines. Sensory analysis also showed that carboxymethylcellulose doesn't have a significant impact on wine sensory attributes. Carboxymethylcellulose doesn't decrease the colouring matter stability. The use of turbidity for evaluating the colouring matter stability of wines has severe drawbacks as the turbidity value measured might not be related to the amount of suspended material. Therefore, the application of carboxymethylcellulose in red wines is efficient in increasing tartaric stability without impacting on the phenolic composition, sensory characteristics, and colouring matter stability.

Alternative Methods for Measuring the Susceptibility of White Wines to Pinking Alteration: Derivative Spectroscopy and CIEL*a*b* Colour Analysis.

Pinking is the term used for describing the pink colouration that appears in white wines produced under reducing conditions when oxidised. The ability to predict the susceptibility of white wines for pinking is of utmost importance for wine producers. In this work, we critically compare the two most currently used methods for measuring pinking susceptibility and the use of the first derivative spectra and the CIEL*a*b* colour space method. The amplitude of the first derivative spectra in the 450-550 nm range has a good correlation with the values obtained by subtracting the extrapolate background at 500 nm (R2 = 0.927); therefore, first derivative spectroscopy seems to be a more straightforward approach for eliminating the background problem that occurs in this method. The CIEL*a*b* method using the a* value after oxidation seems to be the most appropriate method to measure the pinking susceptibility of white wines, showing a very good correlation with the amplitude of the first derivative spectra. The pink colouration visualisation is linearly related to the b* value of the white wine, showing that no universal cut-off value for predicting the pink visualisation should be used. Second derivative spectra allow the observation of the formation of different chromophores in wines after induced oxidation.

Effect of Pre-Fermentative Maceration and Fining Agents on Protein Stability, Macromolecular, and Phenolic Composition of Albariño White Wines: Comparative Efficiency of Chitosan, k-Carrageenan and Bentonite as Heat Stabilisers.

In this work, the effect of pre-fermentative skin maceration (PFSM) on the chemical composition of the macromolecular fraction, polysaccharides and proteins, phenolic compounds, chromatic characteristics, and protein stability of Albariño monovarietal white wines was studied. PFSM increased the extraction of phenolic compounds and polysaccharides and reduced the extraction of pathogenesis-related proteins (PRPs). PFSM wine showed significantly higher protein instability. Sodium and calcium bentonites were used for protein stabilisation of wines obtained with PFSM (+PFSM) and without PFSM (-PFSM), and their efficiencies compared to fungal chitosan (FCH) and k-carrageenan. k-Carrageenan reduced the content of PRPs and the protein instability in both wines, and it was more efficient than sodium and calcium bentonites. FCH was unable to heat stabilise both wines, and PRPs levels remained unaltered. On the other hand, FCH decreased the levels of wine polysaccharides by 60%. Sodium and calcium bentonite also decreased the levels of wine polysaccharides although to a lower extent (16% to 59%). k-Carrageenan did not affect the wine polysaccharide levels. Overall, k-carrageenan is suitable for white wine protein stabilisation, having a more desirable impact on the wine macromolecular fraction than the other fining agents, reducing the levels of the wine PRPs without impacting polysaccharide composition.

An accurate single-step LLE method using keeper solvent for quantification of trace amounts of sotolon in Port and white table wines by HPLC-DAD.

Sotolon has been reported to play an important role in the typical aroma of aged Port wines. A simple and cheap single-step liquid-liquid extraction (LLE) using glycerol as a keeper for liquid chromatography/ultra-violet absorption quantification of sotolon in Port wines is proposed in this work. The glycerol plays a protective role during the concentration of the extracts increasing the sotolon recovery as well the method repeatability. The proposed method yields chromatograms without interfering compounds and a forty-fold enrichment of sotolon. The detection and quantification limits were far below the sotolon odour threshold in Port wine (19 µg/L). The method was also validated for dry white table wines with good validation parameters. The methodology was successfully applied to selected commercial Tawny, Ruby, and White Port wines, being reported the presence of sotolon in young Ruby and White Port wines for the first time, although below the olfactory detection threshold.

Terroir Effect on the Phenolic Composition and Chromatic Characteristics of Mencía/Jaen Monovarietal Wines: Bierzo D.O. (Spain) and Dão D.O. (Portugal).

'Mencía'/'Jaen' it's an important red grape variety, exclusive of the Iberian Peninsula, used in wine production namely in Bierzo D.O. and Dão D.O., respectively. This work evaluates the effect of the two different "terroirs" on the phenolic composition and chromatic characteristics of 'Mencía'/'Jaen' monovarietal wines produced at an industrial scale in the same vintage. Using Principal Component Analysis (PCA), Partial Least Squares-Discrimination Analysis (PLS-DA), and Orthogonal PLS-DA (OPLS-DA) it was found that peonidin-3-coumaroylglucoside, petunidin-3-glucoside, malvidin-3-coumaroylglucoside, peonidin-3-glucoside, malvidin-3-acetylglucoside, malvidin-3-glucoside, and ferulic acid were the phenolic compounds with the highest differences between the two regions. PLS regression allowed to correlate the differences in lightness (L*) and redness (a*) of wines from 'Jaen' and 'Mencía' to differences in colored anthocyanins, polymeric pigments, total pigments, total anthocyanins, cyanidin-3-acetylglucoside, delphinidin-3-acetylglucoside, delphinidin-3-glucoside, peonidin-3-coumaroylglucoside, petunidin-3-glucoside and malvidin-3-glucoside in wines, and the colorless ferulic, caffeic, and coutaric acids, and ethyl caffeate. The wines a* values were more affected by colored anthocyanins, ferulic acid, total anthocyanins, delphinidin-3-acetylglucoside, delphinidin-3-glucoside and petunidin-3-acetylglucoside, and catechin. The positive influence of ferulic acid in the a* values and ferulic, caffeic, coutaric acids, and ethyl caffeate on the L* values can be due to the co-pigmentation phenomena. The higher dryness and lower temperatures during the September nights in this vintage might explain the differences observed in the anthocyanin content and chromatic characteristics of the wines.

Elimination of Aflatoxins B1 and B2 in White and Red Wines by Bentonite Fining. Efficiency and Impact on Wine Quality.

Aflatoxins B1 and B2 are two highly toxic mycotoxins that have been sometimes found in wines. Currently, no technological solution is available to reduce or eliminate aflatoxins from wines when they are present. Therefore, this work aims to study the efficiency of already approved wine fining agents like activated carbon, potassium caseinate, chitosan, and bentonite for aflatoxins B1 and B2 removal from white and red wines. It was observed that the fining agents' efficiency in removing aflatoxins was dependent on the wine matrix, being higher in white than in red wine. Bentonite was the most efficient fining agent, removing both aflatoxins (10 µg/L total) from the white wine and 100% of aflatoxin B1 and 82% of aflatoxin B2 from red wine. The impact of bentonite on white wine chromatic characteristics was low (color difference, ΔE* = 1.35). For red wine, bentonite addition caused a higher impact on wine' chromatic characteristics (ΔE* = 4.80) due to the decrease in total anthocyanins, although this decrease was only 1.5 points of color intensity. Considering the high efficiency of bentonite in aflatoxins B1 and B2 removal and despite the impact on red wine color, bentonite is a very good technological solution for aflatoxin removal in white and red wines.

New molecularly imprinted polymers for reducing negative volatile phenols in red wine with low impact on wine colour.

4-Ethylphenol (4-EP) and 4-ethylguaiacol (4-EG) formation in red wines by Dekkera/Brettanomyces yeasts reduce significantly wine consumer's acceptability. Polymers with specific adsorption for volatile phenols (VPs) could be a valuable tool for wine producers for removing this negative sensory defect. In this work, a new molecularly imprinted polymer (MIP) was synthesised using ethylene glycol dimethacrylate (EDMA) as cross-linker and ethylene glycol methyl ether acrylate as functional monomers. Although there was observed a competitive binding of the more abundant structurally related phenolic compounds of the wine matrix, it was still able to reduce 38 to 63% the wine VPs, depending on the wine VPs levels, presenting higher performance than the respective non-imprinted polymers (NIP). Sensory analysis of the MIP treated wine resulted in a significant decrease in the phenolic attribute and significant increase of the fruity and floral attributes, with no significant differences in the wine colour perceived by the expert panel. The sensory improvement of the MIP was significantly higher than that observed for the correspondent NIP.

4-Ethylphenol, 4-ethylguaiacol and 4-ethylcatechol in red wines: Microbial formation, prevention, remediation and overview of analytical approaches.

The presence of 4-ethylphenol, 4-ethylguaiacol and 4-ethylcatechol in red wines affect negatively their aroma conferring horsy, barnyard, smoky and medicinal aromatic notes. These volatile phenols formed from free hydroxycinnamic acids and their ethyl esters by Dekkera/Brettanomyces yeasts, can contaminate wines. Their formation can cause serious negative economic impact to the wine industry worldwide as consumers tend to reject these wines. For these reasons various preventive and remedial treatments have been studied. This review summarises the wine microbial volatile phenols formation, preventive measures during winemaking and remedial treatments in finished wines along with their advantages and limitations for dealing with this sensory defect and impact on wine quality. Also it is important to control the levels of volatile phenols in wines using fast and convenient analytical methods namely with a detection limit below their olfactory perception threshold. The analytical methods available for quality control and performance characteristics as well their advantages and disadvantages when dealing with a complex matrix like wine are discussed in detail.

A simple dispersive solid phase extraction clean-up/concentration method for selective and sensitive quantification of biogenic amines in wines using benzoyl chloride derivatisation.

A simple, quick, cheap and green dispersive solid phase extraction (dSPE) method followed by benzoyl chloride pre-column derivatisation for HPLC-UV determination of twelve biogenic amines (BAs) in wines is proposed for the first time. The dSPE using a strong cation exchange resin increased the selectivity and sensitivity of the analysis by elimination of interfering compounds and a five-fold enrichment of BAs. The method presented an adequate precision and linearity with detection limits ranging from 0.133 to 0.509 mg/L. Recoveries ranging from 72 to 99% prove the accuracy of the method for determining BAs in red, white and Tawny Port wine samples yielding chromatograms clean from interferents. The method was applied successfully to the analysis of 31 young red wines from different Portuguese wine regions. The dSPE method although has a potential of broader application to other food matrixes, other derivatisation procedures than benzoyl chloride and other detectors.

Data on changes in red wine phenolic compounds and headspace aroma compounds after treatment of red wines with chitosans with different structures.

Data in this article presents the changes on phenolic compounds and headspace aroma abundance of a red wine spiked with 4-ethylphenol and 4-ethylguaiacol and treated with a commercial crustacean chitin (CHTN), two commercial crustacean chitosans (CHTB, CHTD), one fungal chitosan (CHTF), one additional chitin (CHTNA) and one additional chitosan (CHTC) produced by alkaline deacetylation of CHTN and CHTB, respectively. Chitin and chitosans presented different structural features, namely deacetylation degree (DD), average molecular weight (MW), sugar and mineral composition ("Reducing the negative sensory impact of volatile phenols in red wine with different chitosan: effect of structure on efficiency" (Filipe-Ribeiro et al., 2018) [1]. Statistical data is also shown, which correlates the changes in headspace aroma abundance of red wines with the chitosans structural features at 10 g/h L application dose.

Reducing the negative sensory impact of volatile phenols in red wine with different chitosans: Effect of structure on efficiency.

"Brett character" is a negative sensory attribute acquired by red wines when contaminating Dekkera/Brettanomyces yeasts produce 4-ethylphenol and 4-ethylguaiacol, known as volatile phenols (VPs), from cinnamic acid precursors. In this study, chitins and chitosans with different structural features, namely deacetylation degree (5-91%) and molecular weight (24-466kDa) were used for the reduction of this sensory defect. Chitins and chitosans decreased 7-26% of the headspace abundance of VPs without changing their amounts in wines. The efficiency of reduction increased with the deacetylation degree and applied dose. Reduction of headspace abundance of VPs by chitosans enabled significant decreases in the negative phenolic and bitterness attributes and increased positive fruity and floral attributes. Results show that chitosan with high deacetylation degrees, including fungal chitosan, which is already approved for use in wines, is an efficient approach for reducing the negative sensory impact of VPs in red wines.

Data on changes in red wine phenolic compounds, headspace aroma compounds and sensory profile after treatment of red wines with activated carbons with different physicochemical characteristics.

Data in this article presents the changes on phenolic compounds, headspace aroma composition and sensory profile of a red wine spiked with 4-ethylphenol and 4-ethylguaiacol and treated with seven activated carbons with different physicochemical characteristics, namely surface area, micropore volume and mesopore volume ("Reduction of 4-ethylphenol and 4-ethylguaiacol in red wine by activated carbons with different physicochemical characteristics: impact on wine quality" Filipe-Ribeiro et al. (2017) [1]). Data on the physicochemical characteristics of the activated carbons are shown. Statistical data on the sensory expert panel consistency by General Procrustes Analysis is shown. Statistical data is also shown, which correlates the changes in chemical composition of red wines with the physicochemical characteristics of activated carbons used.

Reduction of 4-ethylphenol and 4-ethylguaiacol in red wine by activated carbons with different physicochemical characteristics: Impact on wine quality.

Activated carbon (AC) could be a solution to remove 4-ethylphenol (4-EP) and 4-ethylguaiacol (4-EG) off-flavours from Dekkera/Brettanomyces contaminated red wines. The relation between AC physicochemical characteristics and removal efficiency of these compounds is unknown. The impact of ACs characteristics on 4-EP and 4-EG removal, phenolic and headspace aroma composition was studied. All ACs reduced significantly 4-EP and 4-EG levels (maximum 73%). Their efficiency was related to their surface area and micropores volume. A higher surface area of mesopores and total pore volume were detrimental for anthocyanins and colour intensity, while a higher surface area and micropores volume were important for removing phenolic acids. Volatile phenols reduction was more important for the positive fruity attribute perception than the abundance of headspace aroma compounds. With an optimal selection of the AC physicochemical characteristics it was possible to remove efficiently the volatile phenols without impacting negatively on the wine sensory quality.