Effect of low molecular weight phenols on the in-mouth sensory perception of high molecular weight phenols by analyzing reconstituted wines.

This research aimed to assess the contribution of monomeric phenols to the perception of bitterness and astringency by means of wine reconstitution experiments. Six wines with distinct total polyphenol indexes were selected and fractioned by preparative liquid chromatography into two fractions. Thirty-one reconstituted wines were prepared by combining distinct low molecular weight fractions (L) with different high molecular weight fractions (H). In-mouth attributes of reconstituted and reference wines were described by a trained sensory panel. Fractions were chemically characterized by UPLC-MS. No significant differences among sensory results were found between reference and reconstituted wines. Bitterness and astringency perception were strongly influenced by total proanthocyanidins content. Flavan-3-ol monomers and dimers were only responsible for astringency in wines with a low content of proanthocyanidins, as was the case in rosé wine. Quercetin-3-O-glucuronide and several anthocyanins presented correlations with bitterness in the reconstituted wines; notwithstanding, several interactions with this attribute were observed.

Synthesis and evaluation of esters obtained from phenols and phenoxyacetic acid with significant phytotoxic and cytogenotoxic activities.

There is a growing demand for herbicides that are more effective than conventional ones yet less harmful to ecosystems. In light of this, this study aimed to synthesize esters from phenols and phenoxyacetic acid, using compounds with known phytotoxic potential as starting materials. Phenoxyacetic acid was first synthesized and then utilized in the synthesis of seven esters through Steglich esterification, employing N,N'-dicyclohexylcarboimide and N,N-dimethylpyridin-4-amine in the presence of phenols (thymol, vanillin, eugenol, carvacrol, guaiacol, p-cresol, and ß-naphthol), yielding esters 1-7. All synthesized compounds were characterized using mass spectrometry, 1H, and 13C NMR. These compounds were tested for phytotoxicity to evaluate their effects on the germination and root development of Sorghum bicolor and Lactuca sativa seeds, and for the induction of alterations in the mitotic cycle of meristematic cells of L. sativa roots. Esters 1, 3, 4, and 5 exhibited the most significant phytotoxic activity in both L. sativa and S. bicolor. Alterations in the mitotic index and frequency of chromosomal alterations in L. sativa roots revealed the cytotoxic, genotoxic effects, and the aneugenic mode of action of the tested molecules. These findings suggest that these compounds could serve as inspiration for the synthesis of new semi-synthetic herbicides.

Characterization and quantification of peptaibol produced by novel Trichoderma spp: Harnessing their potential to mitigate moisture stress through enhanced biochemical and physiological responses in black pepper (Piper nigrum L.).

Trichoderma spp. is primarily applied to manage biotic stresses in plants. Still, they also can mitigate abiotic stresses by the stimulation of antioxidative protective mechanisms and enhanced synthesis of secondary metabolites. The study optimized the conditions to enhance peptaibol production by novel Trichoderma spp, characterized and quantified peptaibol- alamethicin using HPLC and LC MS-MS. The present study investigated these isolates efficacy in enhancing growth and the associated physio-biochemical changes in black pepper plants under moisture stress. Under in vitro conditions, out of 51 isolates studied, six isolates viz., T. asperellum (IISR NAIMCC 0049), T. erinaceum (IISR APT1), T. harzianum (IISR APT2), T. harzianum (IISR KL3), T. lixii (IISR KA15) and T. asperellum (IISR TN3) showed tolerance to low moisture levels (5, 10 and 20%) and higher temperatures (35 and 40 °C). In vivo evaluation on black pepper plants maintained under four different moisture levels (Field capacity [FC]; 75%, 50%, and 25%) showed that the plants inoculated with Trichoderma accumulated greater quantities of secondary metabolites viz., proline, phenols, MDA and soluble proteins at low moisture levels (50% and 25% FC). In the present study, plants inoculated with T. asperellum and T. harzianum showed significantly increased growth compared to uninoculated plants. The shortlisted Trichoderma isolates exhibited differences in peptaibol production and indicated that the peptide might be the key factor for their efficiency as biocontrol agents. The present study also demonstrated that Trichoderma isolates T. harzianum and T. asperellum (IISR APT2 & NAIMCC 0049) enhanced the drought-tolerant capabilities of black pepper by improving plant growth and secondary metabolite production.

Targeting PAR2-mediated inflammation in osteoarthritis: a comprehensive in vitro evaluation of oleocanthal's potential as a functional food intervention for chondrocyte protection and anti-inflammatory effects.

BACKGROUND: Osteoarthritis (OA) is a prevalent degenerative joint disease characterized by chronic inflammation and progressive cartilage degradation, ultimately leading to joint dysfunction and disability. Oleocanthal (OC), a bioactive phenolic compound derived from extra virgin olive oil, has garnered significant attention due to its potent anti-inflammatory properties, which are comparable to those of non-steroidal anti-inflammatory drugs (NSAIDs). This study pioneers the investigation into the effects of OC on the Protease-Activated Receptor-2 (PAR-2) mediated inflammatory pathway in OA, aiming to validate its efficacy as a functional food-based therapeutic intervention. METHODS: To simulate cartilage tissue in vitro, human bone marrow-derived mesenchymal stem cells (BMSCs) were differentiated into chondrocytes. An inflammatory OA-like environment was induced in these chondrocytes using lipopolysaccharide (LPS) to mimic the pathological conditions of OA. The therapeutic effects of OC were evaluated by treating these inflamed chondrocytes with various concentrations of OC. The study focused on assessing key inflammatory markers, catabolic enzymes, and mitochondrial function to elucidate the protective mechanisms of OC. Mitochondrial function, specifically mitochondrial membrane potential (ΔΨm), was assessed using Rhodamine 123 staining, a fluorescent dye that selectively accumulates in active mitochondria. The integrity of ΔΨm serves as an indicator of mitochondrial and bioenergetic function. Additionally, Western blotting was employed to analyze protein expression levels, while real-time polymerase chain reaction (RT-PCR) was used to quantify gene expression of inflammatory cytokines and catabolic enzymes. Flow cytometry was utilized to measure cell viability and apoptosis, providing a comprehensive evaluation of OC's therapeutic effects on chondrocytes. RESULTS: The results demonstrated that OC significantly downregulated PAR-2 expression in a dose-dependent manner, leading to a substantial reduction in pro-inflammatory cytokines, including TNF-α, IL-1ß, and MCP-1. Furthermore, OC attenuated the expression of catabolic markers such as SOX4 and ADAMTS5, which are critically involved in cartilage matrix degradation. Importantly, OC was found to preserve mitochondrial membrane potential (ΔΨm) in chondrocytes subjected to inflammatory stress, as evidenced by Rhodamine 123 staining, indicating a protective effect on cellular bioenergetics. Additionally, OC modulated the Receptor Activator of Nuclear Factor Kappa-Β Ligand (RANKL)/Receptor Activator of Nuclear Factor Kappa-Β (RANK) pathway, suggesting a broader therapeutic action against the multifactorial pathogenesis of OA. CONCLUSIONS: This study is the first to elucidate the modulatory effects of OC on the PAR-2 mediated inflammatory pathway in OA, revealing its potential as a multifaceted therapeutic agent that not only mitigates inflammation but also protects cartilage integrity. The preservation of mitochondrial function and modulation of the RANKL/RANK pathway further underscores OC's comprehensive therapeutic potential in counteracting the complex pathogenesis of OA. These findings position OC as a promising candidate for integration into nutritional interventions aimed at managing OA. However, further research is warranted to fully explore OC's therapeutic potential across different stages of OA and its long-term effects in musculoskeletal disorders.

Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH.

Dark aqueous-phase reactions involving the nitrosation and nitration of aromatic organic compounds play a significant role in the production of light-absorbing organic carbon in the atmosphere. This process constitutes a crucial aspect of tropospheric chemistry and has attracted growing research interest, particularly in understanding the mechanisms governing nighttime reactions between phenols and nitrogen oxides. In this study, we present new findings concerning the rapid dark reactions between phenols containing electron-donating groups and inorganic nitrite in acidic aqueous solutions with pH levels <3.5. This reaction generates a substantial amount of nitroso- and nitro-substituted phenolic compounds, known for their light-absorbing properties and toxicity. In experiments utilizing various substituted phenols, we demonstrate that their reaction rates with nitrite depend on the electron cloud density of the benzene ring, indicative of an electrophilic substitution reaction mechanism. Control experiments and theoretical calculations indicate that the nitrosonium ion (NO+) is the reactive nitrogen species responsible for undergoing electrophilic reactions with phenolate anions, leading to the formation of nitroso-substituted phenolic compounds. These compounds then undergo partial oxidation to form nitro-substituted phenols through reactions with nitrous acid (HONO) or other oxidants like oxygen. Our findings unveil a novel mechanism for swift atmospheric nitrosation and nitration reactions that occur within acidic cloud droplets or aerosol water, providing valuable insights into the rapid nocturnal formation of nitrogen-containing organic compounds with significant implications for climate dynamics and human health.

Non-sulfonamide bacterial CA inhibitors.

Non-sulfonamide chemical moieties able to inhibit the bacterial (b) expressed Carbonic Anhydrases (CAs; EC 4.2.1.1) constitute an important alternative to the prototypic modulators discussed in Chapter 6, as give access to large and variegate chemical classes, also of the natural origin. This contribution reports the main classes of compounds profiled in vitro on the bCAs and thus may be worth developing for the validation process of this class of enzymes.

Nontarget analysis and characterization of p-phenylenediamine-quinones and -phenols in tire rubbers by LC-HRMS and chemical species-specific algorithm.

BACKGROUND: N,N'-disubstituted p-phenylenediamine-quinones (PPDQs) are oxidization derivatives of p-phenylenediamines (PPDs) and have raised extensive concerns recently, due to their toxicities and prevalence in the environment, particularly in water environment. PPDQs are derived from tire rubbers, in which other PPD oxidization products besides reported PPDQs may also exist, e.g., unknown PPDQs and PPD-phenols (PPDPs). RESULTS: This study implemented nontarget analysis and profiling for PPDQ/Ps in aged tire rubbers using liquid chromatography-high-resolution mass spectrometry and a species-specific algorithm. The algorithm took into account the ionization behaviors of PPDQ/Ps in both positive and negative electrospray ionization, and their specific carbon isotopologue distributions. A total of 47 formulas of PPDQ/Ps were found and elucidated with tentative or accurate structures, including 25 PPDQs, 18 PPDPs and 4 PPD-hydroxy-quinones (PPDHQs). The semiquantified total concentrations of PPDQ/Ps were 14.08-30.62 µg/g, and the concentrations followed the order as: PPDPs (6.48-17.39) > PPDQs (5.86-12.14) > PPDHQs (0.16-1.35 µg/g). SIGNIFICANCE: The high concentrations and potential toxicities indicate that these PPDQ/Ps could seriously threaten the eco-environment, as they may finally enter the environment, accordingly requiring further investigation. The analysis strategy and data-processing algorithm can be extended to nontarget analysis for other zwitterionic pollutants, and the analysis results provide new understandings on the environmental occurrence of PPDQ/Ps from source and overall perspectives.

Transcriptome analysis reveals activation of detoxification and defense mechanisms in smoke-exposed Merlot grape (Vitis vinifera) berries.

A significant consequence of climate change is the rising incidence of wildfires. When wildfires occur close to wine grape (Vitis vinifera) production areas, smoke-derived volatile phenolic compounds can be taken up by the grape berries, negatively affecting the flavor and aroma profile of the resulting wine and compromising the production value of entire vineyards. Evidence for the permeation of smoke-associated compounds into grape berries has been provided through metabolomics; however, the basis for grapevines' response to smoke at the gene expression level has not been investigated in detail. To address this knowledge gap, we employed time-course RNA sequencing to observe gene expression-level changes in grape berries in response to smoke exposure. Significant increases in gene expression (and enrichment of gene ontologies) associated with detoxification of reactive compounds, maintenance of redox homeostasis, and cell wall fortification were observed in response to smoke. These findings suggest that the accumulation of volatile phenols from smoke exposure activates mechanisms that render smoke-derived compounds less reactive while simultaneously fortifying intracellular defense mechanisms. The results of this work lend a better understanding of the molecular basis for grapevines' response to smoke and provide insight into the origins of smoke-taint-associated flavor and aroma attributes in wine produced from smoke-exposed grapes.

Parental Effect on Agronomic and Olive Oil Traits in Olive Progenies from Reciprocal Crosses.

Olive growing is undergoing a transition from traditional cultivation systems to a more technological model characterized by increased mechanization and a higher density of plants per hectare. This shift implies the use of less vigorous varieties that can adapt to the new system. Most traditional varieties are highly vigorous, and breeding programs can provide solutions to this challenge. This study investigates the parental effect on different agronomic and olive oil characteristics and its role in breeding programs. The objectives were to evaluate and characterize different agronomic and olive oil traits in the progenies from 'Arbosana' × 'Sikitita' cross and its reciprocal cross 'Sikitita' × 'Arbosana'. The results showed a high variability of the characters evaluated in the progenitors of the reciprocal crosses. The highest coefficients of variation were observed in traits related to ripening index, phenolic compounds, polyunsaturated fatty acids, and Δ5-avenasterol, with phenolic content exhibiting the greatest variability. No statistically significant maternal effect was detected for any of the evaluated traits, although a slight positive maternal effect was systematically observed in the mean values of the evaluated traits. These results suggest that the maternal effect on olive is quite subtle, although due to a slight tendency of the maternal effect in the descriptive analyses, future studies are suggested to understand in depth the possible maternal effect on olive breeding.

Cytotoxic activity of callus extract from Vachellia farnesiana (L) Wight & Arn.

The in vitro cultures of Vachellia farnesiana (L) Wight & Arn. have demonstrated cytotoxic activity through callus extract on the HeLa cell line. Explants excised from in vitro-grown seedlings from seeds of two different locations were inoculated on Murashige and Skoog (MS) culture media containing various concentrations of N-6 benzyladenine (BA) or kinetin with 2,4-dichlorophenoxyacetic acid (2,4-D). Optimal efficiency in friable callus induction (100%) was achieved in leaf explants cultured on MS media containing 2.32 µM BA + 13.57 µM 2,4-D. Plant tissues (callus and leaf) were extracted and subjected to quantitative phytochemical analysis, revealing the highest total alkaloid and phenolic content in leaf extracts from Queretaro adult specimens (339.5 ± 20.9 mg atropine equivalents (AE) per g dry extract (DE) and 158.4 ± 12.5 mg gallic acid equivalents (GAE) per g DE, respectively). In contrast, callus cultures exhibited significantly higher total triterpene content (356-381 mg ursolic acid equivalents (UAE) per g DE) compared to leaf extracts (208-243 mg UAE/g DE). Both leaf and callus extracts displayed cytotoxic activity against the HeLa cell line, with a significantly lower half-maximal inhibitory concentration (IC50) for leaf extracts (28-32 µg/mL) compared to callus cultures (43-66 µg/mL), suggesting that alkaloids were primarily responsible for the cytotoxic activity. Furthermore, this study provides valuable insights into the controlled production of bioactive compounds with cytotoxic activity, with callus serving as a rich source.

Microbial catabolism of coffee pulp (poly)phenols during in vitro colonic fermentation.

Coffee pulp is a by-product characterized by its richness in phenolic compounds. This study examined the catabolism of (poly)phenols in digested coffee pulp flour (CPF) and extract (CPE) during in vitro colonic fermentation. After a simulated gastrointestinal digestion, samples were fermented using human microbiota and (poly)phenol transformations were analyzed by UHPLC-ESI-MS/MS. Digested CPF and CPE contained high amounts of phenolic acids, notably 3',4'-dihydroxycinnamic (99.7-240.1 µmol 100 g-1) and 3,4-dihydroxybenzoic acid (174.1-491.4 µmol 100 g-1). During the in vitro fecal fermentation, phenylpropanoic acids (1.5- to 2.6-fold), phenyl-γ-valerolactones (1.3- to 23-fold), phenylvaleric acids (1.1- to 2-fold) and benzene derivatives (1.5-fold) increased; while benzoic and cinnamic acids, cinnamoylquinic derivatives, flavonols, benzaldehydes and diphenylpropan-2-ols decreased. The (poly)phenols in CPF were catabolized more slowly than in CPE, suggesting protection of the fibrous matrix against phenolic degradation. Coffee pulp may be a promising food ingredient rich in (poly)phenols contributing to the prevention of intestinal diseases.

Antifungal Activity of Phloroglucinol Derivatives against Botrytis cinerea and Monilinia fructicola.

Naturally derived compounds show promise as treatments for microbial infections. Polyphenols, abundantly found in various plants, fruits, and vegetables, are noted for their physiological benefits including antimicrobial effects. This study introduced a new set of acylated phloroglucinol derivatives, synthesized and tested for their antifungal activity in vitro against seven different pathogenic fungi. The standout compound, 3-methyl-1-(2,4,6-trihydroxyphenyl) butan-1-one (2b), exhibited remarkable fungicidal strength, with EC50 values of 1.39 µg/mL against Botrytis cinerea and 1.18 µg/mL against Monilinia fructicola, outperforming previously screened phenolic compounds. When tested in vivo, 2b demonstrated effective antifungal properties, with cure rates of 76.26% for brown rot and 83.35% for gray mold at a concentration of 200 µg/mL, rivaling the commercial fungicide Pyrimethanil in its efficacy against B. cinerea. Preliminary research suggests that 2b's antifungal mechanism may involve the disruption of spore germination, damage to the fungal cell membrane, and leakage of cellular contents. These results indicate that compound 2b has excellent fungicidal properties against B. cinerea and holds potential as a treatment for gray mold.

Catalytic Hydrodeoxygenation of Phenols and Cresols to Gasoline Range Biofuels.

Unlike fossil fuels, biomass has oxygen amounts exceeding 10 wt%. Hydrodeoxygenation (HDO) is a crucial step in upgrading biomass to higher heating value liquid fuels. Oxygen removal has many challenges due to the complex chemistry and the high reactivity leading to irreversible catalyst deactivation. In this study, the focus is on the catalytic HDO of aromatic oxygen-containing model compounds in biomass: phenols and cresols. In the current work, literature on catalytic HDO of phenols using molecular hydrogen is reviewed, with a focus on non-nickel-based mono- and bi-metallic catalysts, as nickel-based catalysts were reviewed elsewhere. In addition, the catalytic HDO of m-cresol using molecular hydrogen is examined. This review also addresses the use of hydrogen donors for the HDO of phenols and cresols. The operating conditions, catalysts, products, and yields are summarized to find the catalyst with promising activity and high selectivity toward aromatics. A critical review of the reactions that successfully led to HDO is presented and research gaps related to the HDO of phenols and cresols are highlighted. The conclusions provide potential successful catalyst combinations that can be used for HDO of phenols, cresols, and liquid aromatic hydrocarbons.

Animal Food Products to Support Human Nutrition and to Boost Human Health: The Potential of Feedstuffs Resources and Their Metabolites as Health-Promoters.

Recent attention has been given to animal feeding and its impact on human nutrition. Animal feeding is essential for meeting human dietary needs, making it a subject of significant interest and investigation. This review seeks to outline the current understanding of this disciplinary area, with a focus on key research areas and their potential implications. The initial part of the paper discusses the importance of animal feed resources and recognizes their crucial role in guaranteeing sufficient nutrition for both humans and animals. Furthermore, we analyzed the categorization of animal feeds based on the guidelines established by the National Research Council. This approach offers a valuable structure for comprehending and classifying diverse types of animal feed. Through an examination of this classification, we gain an understanding of the composition and nutritional content of various feedstuffs. We discuss the major categories of metabolites found in animal feed and their impact on animal nutrition, as well as their potential health advantages for humans. Flavonoids, polyphenols, tannins, terpenoids, vitamins, antioxidants, alkaloids, and essential oils are the primary focus of the examination. Moreover, we analyzed their possible transference into animal products, and later we observed their occurrence in foods from animal sources. Finally, we discuss their potential to promote human health. This review offers an understanding of the connections among the major metabolites found in feedstuffs, their occurrence in animal products, and their possible impact on the health of both animals and humans.

Contribution of distinct components in divergent organic amendments to long-term accumulation of soil organic matter in agricultural soils: evidence from thermally assisted hydrolysis and methylation-GC/MS.

Although maintaining/improving soil organic matter (SOM) quantity through utilizing organic amendments (OAs) is a productive practice, information on OA components contributing to long-term SOM accumulation in agricultural soils remains meager. Hence, we examined soil samples from a long-term experiment with different fertilizer managements, including no fertilizer (NF), chemical fertilizer (CF) only (CF), bark compost plus CF (BC + CF), coffee residue compost plus CF (CRC + CF), cattle manure compost plus CF (CMC + CF), and cattle manure compost (CMC) or sewage sludge compost (SSC) alone at a higher application rate. SOM in those samples was physically fractionated into free particulate form (fSOM), free form occluded in aggregates (oSOM), weakly bound form (wSOM), and strongly bound form (sSOM). Analysis of structural components in OAs and SOM fractions using thermally assisted hydrolysis and methylation combined with gas chromatography/mass spectrometry (THM-GC/MS) revealed OA components that have contributed to long-term SOM accumulation in each treatment. The SSC was characterized by higher proportions of short-chain fatty acids (FAs; 50%) and other aliphatic compounds (22%). Correlation analysis suggested that these characteristics may be effective for greater C accumulation in the bulk soil and wSOM fraction. The proportion of lignin-derived phenols, e.g., 3,4-dimethoxybenzaldehyde (Vh) and 1,2-dimethoxy-4-(1,2,3-trimethoxypropyl)benzene, was high in CMC (43%), presumably vital for promoting C accumulations in the oSOM, wSOM, and sSOM fractions in the CMC treatment. The short-chain FAs in CRC and aromatic components in BC are likely important for contributing fSOM accumulation.

Unveiling the Nutritional Profile and Safety of Coffee Pulp as a First Step in Its Valorization Strategy.

The coffee pulp, a significant by-product of coffee processing, is often discarded but has potential for recycling and high-value uses. This study aimed to investigate the chemical composition of two coffee pulp ingredients, a flour (CPF) and an aqueous extract (CPE), and conducted acute and sub-chronic toxicity assays to determine their safety. The proximate composition revealed the high fiber content of both ingredients; the CPF mainly contained insoluble fiber, while CPE consisted exclusively of soluble pectic polysaccharides. The CPF had higher concentrations of amino acids and a better balance of essential/non-essential amino acids, whereas the CPE exhibited higher concentrations of free amino acids, ensuring higher bioavailability. Both ingredients showed elevated mineral content, while heavy-metal concentrations remained within acceptable limits. This study established the bioactive potential of the CPF and the CPE, demonstrating the high content of caffeine and gallic, protocatechuic, and 4-caffeoylquinic acids. The toxicity studies revealed that the CPF and the CPE exhibited safety when orally administered to mice. Administered doses were non-toxic, as they did not induce lethality or adverse effects in the mice or produce significant histopathological or biochemical adverse changes. This study represents a first step in valorizing the CPF and the CPE as safe novel food ingredients with health benefits for functional and nutritional foods.

Associations between single and combined exposures to environmental phenols and ulcerative colitis in American adults.

OBJECTIVE: The etiology of ulcerative colitis (UC) is complex and involves multiple factors, with exposure to environmental toxins potentially contributing greatly to its pathogenesis. Therefore, this study was carried out with the purpose of delving into the associations between single and combined exposures to environmental phenols and UC among American adults. METHODS: Survey data from the 2009-2010 National Health and Nutrition Examination Survey were selected for our research. The associations between single and combined exposures to environmental phenols and the prevalence of UC were analyzed using weighted multivariate logistic regression models as well as Bayesian kernel machine regression (BKMR). RESULTS: A total of 1,422 adults aged 20 years old and above were included in this study, 17 of whom had UC. The correlation matrix showed strong associations between 2,4-dichlorophenol (2,4-DCP) and 2,5-dichlorophenol (2,5-DCP) (R = 0.81), as well as between 2,4,5-trichlorophenol (2,4,5-TCP) and 2,4,6-trichlorophenol (2,4,6-TCP) (R = 0.73). The logistic regression model revealed that, after adjusting for confounders, exposure to environmental phenols was positively associated with the prevalence of UC, with 2,4,6-TCP showing a significant association (OR = 2.37, 95 % CI = 1.10, 5.09, P = 0.037). The BKMR analysis indicated an upward trend in the overall effect of combined exposures to environmental phenols on UC. All five phenols contributed to this effect, with 2,4,6-TCP exhibiting the most pronounced effect. When other compounds were fixed at the 50th percentile, the impact of the five phenols on UC demonstrated a positive association, without any noteworthy interaction among the compounds. CONCLUSION: Our findings suggested that exposure to environmental phenols may contribute to the occurrence of UC among American adults.

Evaluation of passive samplers as a cost-effective method to predict the impact of wildfire smoke in grapes and wines.

Wildfire smoke exposure alters grape composition, potentially resulting in "smoke tainted" wines. This has been correlated with elevated levels of smoke-derived volatile phenols (VPs) in grapes and wines. This work sought to create a predictive tool that could correlate levels of VPs in smoke with concentrations in grapes and wines. Therefore, passive samplers and Cabernet Sauvignon grapes were intentionally exposed to various smoke intensities, and wines were made thereafter. As expected, concentrations of VPs in grapes and wines were positively associated with the intensity of smoke exposure. Interestingly, levels of guaiacol in the passive samplers had a strong positive correlation with concentrations in grapes (R2 = 0.9999) and wines (R2 = 0.9998). The passive samplers were able to accurately predict guaiacol levels in smoke exposed grapes and wines with percent errors ranging from 0.08 to 11.3 %. These results suggest the capability of passive samplers to act as a monitoring system in vineyards during smoke events.

Blue maize with pigmented germ: Phytochemical compounds and tortilla color.

Blue maize is used in the production of various traditional foods, and its phytochemical composition has been claimed to possess health benefits. In this study, two blue maize hybrids with pigmented germ grown in five environments were studied under the hypothesis that the germ could have a different anthocyanin profile from that of anthocyanins synthesized in the aleurone layer, and that those in the germ could increase the total anthocyanin content in the whole grain. The percentage of pigmented germ, total anthocyanin content (TA) and total soluble phenols in the germ, whole grain and tortilla were evaluated to determine how tortilla color is modified. For the first time, the anthocyanin and fatty acid profiles of pigmented germ were determined. In the anthocyanin profile, anthocyanins derived from peonidin stood out, making 50.7 %. The most abundant fatty acid was linoleic acid (40.6 %). Whole kernel TA content increased when the maize had a higher percentage of pigmented germ, with minimal changes when grain was transformed to tortilla, resulting in darker tortillas. The large variation in TA among environments highlights the importance of identifying the environments that most favor anthocyanin synthesis.

Proton vs Electron: The Dual Role of Redox-Inactive Metal Ions in Permanganate Oxidation Kinetics.

Redox-inactive metal-ion-driven modulation of the oxidation behavior of high-valent metal-oxo complex has garnered significant interest in biological and chemical synthesis; however, their role in permanganate (Mn(VII)) oxidation for the removal of organic pollutants has been largely neglected. Here, we uncover the impact of six metal ions (i.e., Ca2+, Mg2+, Ni2+, Zn2+, Al3+, and Sc3+) presenting in water environments on Mn(VII) activity. These ions uniformly boost the electron and oxygen transfer capabilities of Mn(VII) while impeding proton transfer, as evidenced by electrochemical tests, thioanisole probe analysis, and the kinetic isotope effect. The observed effects are intricately linked to the Lewis acidity of the metal ions. Further mechanistic insights reveal that Mn(VII) can interact with metal ions without direct reduction. Such interactions modify the electronic configuration of Mn(VII) and create an acidic microenvironment, thus increasing its electrophilicity and the energy barrier for the abstraction of proton from organic substrates. More importantly, the efficacy of Mn(VII) in removing phenolic pollutants is regulated by these ions through changing the driving force for proton and electron transfer, i.e., facilitated at pH > 4.5 and inhibited at lower pH. The contribution of active Mn intermediates is also discussed to reveal the oxidative mechanism of the metal ion/Mn(VII) system. These findings not only facilitate the rational design of Mn(VII) oxidation conditions in the presence of metal ions for water decontamination but also offer an alternative paradigm for enhancing electrophilic oxidation.