Volatile aroma compound-based decoding and prediction of sweet berry aromas in dry red wine.

To explore the volatile markers of typical sweet berry flavors in dry red wine, Marselan, Cabernet Sauvignon, Merlot, and Cabernet Franc wines were pretreated using solid-phase microextraction (SPME) and liquid-liquid extraction-solvent-assisted flavor evaporation (LLE-SAFE), and key odorants were analyzed using sensomics approach. Results indicated that Marselan wines exhibited intense sweet berry aromas compared to other varieties wines. Omission tests on one- and four-year-aged wines identified ß-damascenone, isoamyl acetate, 2,3-butanediol, phenylethanol as sweet aroma markers, while geranyl acetone, ethyl isobutyrate, ethyl 2-methylbutyrate as berry aroma markers, which were verified by partial least squares regression. Meanwhile, optimal flavor intensity prediction models between sweet/berry aroma and volatile markers natural logarithms concentration were created with all wines. Moreover, consistent with aroma intensity, most berry markers content increased during aging while sweet markers decreased. This study completes the analytical methodology for volatile markers of wine typical aroma and provides theoretical support for wine flavor prediction.

Asymmetric Paired Electrolysis: Enantioselective Alkylation of Sulfonylimines via C(sp3)-H Functionalization.

Enantioselective transformation of ubiquitous C(sp3)-H bonds into three-dimensional chiral scaffolds is of longstanding interest to synthetic chemists. Herein, an asymmetric paired electrolysis enables a highly efficient and sustainable approach to the enantioselective alkylation of sulfonylimines via C(sp3)-H functionalization. In this protocol, anodic oxidation for benzylic radical formation and Lewis acid-catalyzed sulfonylimine reduction on the cathode were seamlessly cross-coupled (up to 88 % yield). Enantioenriched chiral amines containing a tetrasubstituted carbon stereocenter are accessed with high enantioselectivity (up to 96 % ee). Mechanistic studies suggest that the amine generated in situ could serve as a base to deprotonate phenols and decrease the oxidation potential of the reaction, allowing phenols with lower potentials to be preferentially oxidized.

Photoelectrochemical Fe/Ni cocatalyzed C-C functionalization of alcohols.

The simultaneous activation of reactants on the anode and cathode via paired electrocatalysis has not been extensively demonstrated. This report presents a paired oxidative and reductive catalysis based on earth-abundant iron/nickel cocatalyzed C-C functionalization of ubiquitous alcohols. A variety of alcohols (i.e., primary, secondary, tertiary, or unstrained cyclic alcohols) can be activated at very low oxidation potential of (~0.30 V vs. Ag/AgCl) via photoelectrocatalysis coupled with versatile electrophiles. This reactivity yields a wide range of structurally diverse molecules with broad functional group compatibility (more than 50 examples).

Gallic acid improves color quality and stability of red wine via physico-chemical interaction and chemical transformation as revealed by thermodynamics, real wine dynamics and benchmark quantum mechanical calculations.

The aim of this study was to explore the copigmentation effect of gallic acid on red wine color and to dissect its mechanism at the molecular level. Three-dimensional studies, e.g., in model wine, in real wine and in silico, and multiple indicators, e.g., color, spectrum, thermodynamics and phenolic dynamics, were employed. The results showed that gallic acid significantly enhanced the color quality and stability of red wine. Physico-chemical interactions and chemical transformations should be the most likely mechanism, and physico-chemical interactions are also a prerequisite for chemical transformations. QM calculations of the physico-chemical interactions proved that the binding between gallic acid and malvidin-3-O-glucoside is a spontaneous exothermic reaction driven by hydrogen bonding and dispersion forces. The sugar moiety of malvidin-3-O-glucoside and the phenolic hydroxyl groups of gallic acid affect the formation of hydrogen bonds, while the dispersion interaction was related to the stacking of the molecular skeleton.

Improving aromatic higher alcohol acetates in wines by co-fermentation of Pichia kluyveri and Saccharomyces cerevisiae: growth interaction and amino acid competition.

BACKGROUND: Higher alcohol acetates (HAAs) are potent aroma-active esters that impart desirable fruity and floral aromas. However, the conversion of higher alcohol precursors into HAAs is extremely low in winemaking. To investigate the underlying yeast-yeast interaction on targeted improvement of aromatic HAAs, we evaluated fermentation activity, cell viability, amino acid consumption and HAA production when Pichia kluyveri and Saccharomyces cerevisiae were inoculated concurrently or sequentially. RESULTS: Pichia kluyveri PK-21 possessed the ability to survive and increased HAA level up to 5.2-fold in mixed fermentation. Such an increment may benefit from the efficient conversion of higher alcohol precursors into HAAs (>27-fold higher than S. cerevisiae). During mixed fermentation, the two yeasts exhibited crucial interactions regarding cell growth and amino acid competition. Saccharomyces cerevisiae dominated over the co-inoculated P. kluyveri by efficient uptake of amino acids and biomass production. However, this dominance decreased in sequential fermentation, where P. kluyveri growth increased due to the consumption of preferred amino acids prior to S. cerevisiae. Pearson correlation analysis indicated that phenylalanine and aspartic acid may act as positive amino acids in boosting P. kluyveri growth and HAA production. Laboratory-scale winemaking validated the fermentation performance of P. kluyveri in sequential inoculum, resulting in a balanced aroma profile with enhanced floral and tropical fruity characteristics in the final wines. CONCLUSION: This study proposes a microbial, non-genetically engineered approach for targeted increase of HAA production in winemaking and the findings provide new insights into yeast-yeast interactions. © 2024 Society of Chemical Industry.

Decoding Polysaccharides from Two Pichia Yeasts and Their Molecular Interaction with Wine Fruity Esters.

This study extensively characterized yeast polysaccharides (YPs) from Pichia fermentans (PF) and Pichia kluyveri (PK), with a specific focus on their structural attributes and their interaction with wine fruity esters in a model wine system. By finely tuning enzymatic reactions based on temperature, pH, and enzyme dosage, an optimal YP yield of 77.37% was achieved, with a specific mass ratio of cellulase, pectinase, and protease set at 3:5:2. There were four YP fractions (YPPF-W, YPPF-N, YPPK-W, and YPPK-N) isolated from the two yeasts. YPPF-N and YPPK-N were identified as glucans based on monosaccharide analysis and Fourier-transform infrared spectroscopy analysis. "Specific degradation-methylation-nuclear magnetic" elucidated YPPF-W's backbone structure as 1,3-linked α-l-Man and 1,6-linked α-d-Glc residues, while YPPK-W displayed a backbone structure of 1,3-linked α-Man residues, indicative of a mannoprotein nature. Isothermal titration calorimetry revealed spontaneous interactions between YPPK-W/YPPF-W and fruity esters across temperatures (25-45 °C), with the strongest interaction observed at 30 °C. However, distinct esters exhibited varying interactions with YPPK-W and YPPF-W, attributed to differences in molecular weights and hydrophobic characteristics. While shedding light on these intricate interactions, further experimental data is essential for a comprehensive understanding of yeast polysaccharides' or mannoproteins' impact on fruity esters. This research significantly contributes to advancing our knowledge of yeast polysaccharides' role in shaping the nuanced sensory attributes of wine.

Intermolecular interactions between malvidin-3-O-glucoside and caffeic acid: Structural and thermodynamic characterization and its effect on real wine color quality.

The copigmentation effect between malvidin-3-O-glucoside and caffeic acid was comprehensive inquiry on the model wine solution, theoretical simulation and real wine. Thermodynamic parameters were determined by UV/Visible spectroscopy and Isothermal titration calorimetry (ITC). Theoretical data were obtained employing a dispersion-corrected density functional approach. The effects in real wines were investigated by adding the caffeic acid during different fermentation periods. Results shown that the copigmentation reaction between caffeic acid and malvidin-3-O-glucoside is a spontaneous exothermic reaction driven by hydrogen bonding and dispersions forces. Computations show that the polyhydroxyl sugar moiety and phenolic hydroxyl groups are the key active sites. The addition of caffeic acid in post-alcohol fermentation samples evidences an improving color characteristics in the wine.

Asymmetric Paired Electrocatalysis: Enantioselective Olefin-Sulfonylimine Coupling.

Asymmetric electrocatalysis offers exciting new strategies for the synthesis of chiral molecules through novel reaction pathways. However, simultaneous activation of reactants on both electrodes via asymmetric paired electrolysis, which is more energy efficient and economic than single half-electrode synthesis, remains a formidable challenge. Herein, an asymmetric olefin-sulfonylimine coupling via paired electrocatalysis is presented for the first time. In this protocol, Co-catalyzed hydrogen atom transfer on the anode and Ni-catalyzed sulfonylimine reduction on the cathode were seamlessly cross-coupled. The new catalytic system enables the formation of chiral amine products bearing a tetrasubstituted carbon stereocenter with a high enantioselectivity (up to 96% ee).

Identification and validation of seed dormancy loci and candidate genes and construction of regulatory networks by WGCNA in maize introgression lines.

KEY MESSAGE: Seventeen PHS-QTLs and candidate genes were obtained, including eleven major loci, three under multiple environments and two with co-localization by the other mapping methods; The functions of three candidate genes were validated using mutants; nine target proteins and five networks were filtered by joint analysis of GWAS and WGCNA. Seed dormancy (SD) and pre-harvest sprouting (PHS) affect yield, as well as grain and hybrid quality in seed production. Therefore, identification of genetic and regulatory pathways underlying PHS and SD is key to gene function analysis, allelic variation mining and genetic improvement. In this study, 78,360 SNPs by SLAF-seq of 230 maize chromosome segment introgression lines (ILs), PHS under five environments were used to conduct GWAS (genome wide association study) (a threshold of 1/n), and seventeen unreported PHS QTLs were obtained, including eleven QTLs with PVE > 10% and three QTLs under multiple environments. Two QTL loci were co-located between the other two genetic mapping methods. Using differential gene expression analyses at two stages of grain development, gene functional analysis of Arabidopsis mutants, and gene functional analysis in the QTL region, seventeen PHS QTL-linked candidate genes were identified, and their five molecular regulatory networks constructed. Based on the Arabidopsis T-DNA mutations, three candidate genes were shown to regulate for SD and PHS. Meanwhile, using RNA-seq of grain development, the weighted correlation network analysis (WGCNA) was performed, deducing five regulatory pathways and target genes that regulate PHS and SD. Based on the conjoint analysis of GWAS and WGCNA, four pathways, nine target proteins and target genes were revealed, most of which regulate cell wall metabolism, cell proliferation and seed dehydration tolerance. This has important theoretical and practical significance for elucidating the genetic basis of maize PHS and SD, as well as mining of genetic resources and genetic improvement of traits.

Synergy Effect between Fruity Esters and Potential Odorants on the Aroma of Hutai-8 Rose Wine Revealed by Threshold, S-Curve, and σ-τ Plot Methods.

To analyze the contribution of fruity esters on wine aroma perception, the interaction levels between 12 esters and key odorants of Hutai-8 rose wine were investigated using threshold, S-curve, and σ-τ plot methods, and the aroma enhancement performance of esters was verified by using addition experiments. Results indicated that esters enhance the sweet, floral, and fruity traits of citronellol, ß-damascenone, and nerolidol, especially at subthreshold levels. Meanwhile, esters increased the floral and fruity characteristics of key fermentative odorants mainly by additive effects, with acetate esters possessing a better synergy ability. In contrast, the synergy levels between binary esters were less influenced by the concentration but more by the compound structure and aroma. Additionally, moderately subjoining the type and content of esters in wine proved that their synergy effects improved the sweet trait and decreased the sour fruit trait. This finding characterized that the contribution of esters to the wine aroma was obtained by the combined synergy of odorants at a suitable concentration.