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Contamination by polycyclic aromatic hydrocarbons (PAHs) is an urgent environmental concern, given its atmospheric dispersion and deposition in water bodies and soils. These compounds and their nitrated and oxygenated derivatives, which can exhibit high toxicities, are prioritized in environmental analysis contexts. Amid the demand for precise analytical techniques, comprehensive two-dimensional chromatography coupled with mass spectrometry (GCxGC/Q-TOFMS) has emerged as a promising tool, especially in the face of challenges like co-elution. This study introduces an innovation in the pre-concentration and detection of PAHs using an extraction fiber based on polydimethylsiloxane (PDMS), offering greater robustness and versatility. The proposed technique, termed in-tube extraction, was developed and optimized to effectively retain PAHs and their derivatives in aqueous media, followed by GCxGC/Q-TOFMS determination. Fiber characterization, using techniques such as TG, DTG, FTIR, and SEM, confirmed the hydrophobic compounds retention properties of the PDMS. The determination method was validated, pointing to a significant advancement in the detection and analysis of PAHs in the environment, and proved effective even for traces of these compounds. The results showed that the detection limits (LOD) and quantification limits (LOQ) ranged from 0.07 ng L-1 to 1.50 ng L-1 and 0.33 ng L-1 to 6.65 ng L-1, respectively; recovery ranged between 72 % and 117 %; and the precision intraday and interday ranged from 1 % to 20 %. The fibers were calibrated in the laboratory, with exposure times for analysis in the equilibrium region ranging from 3 to 10 days. The partition coefficients between PDMS and water were also evaluated, showing logarithm values ranging from 2.78 to 5.98. The fibers were applied to the analysis of real water samples, demonstrating high capacity. Additionally, given the growing demand for sustainable methods, the approach presented here incorporates green chemistry principles, providing an efficient and eco-friendly solution to the current chemical analysis scenario.
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(1) Background: Branched-chain and aromatic amino acids (BCAAs/AAAs) have been considered as markers of type 2 diabetes (T2D); however, studies on associations between these metabolites and T2D and cardiometabolic traits in Hispanic populations are limited. The aim of this study was to examine the associations between baseline BCAAs (isoleucine, leucine, valine)/AAAs (phenylalanine, tyrosine) and prevalent and incident T2D, as well as baseline and longitudinal (2 year) changes in cardiometabolic traits (measures of glycemia, dyslipidemia, inflammation, and obesity) in two large cohorts of adults of Puerto Rican descent. (2) Methods: We included participants of the Boston Puerto Rican Health Study (BPRHS, n = 670) and San Juan Overweight Adult Longitudinal study (SOALS, n = 999) with available baseline metabolite and covariate data. T2D diagnosis was defined based on American Diabetes Association criteria. Multivariable logistic (for baseline T2D), Poisson (for incident T2D), and linear (for cardiometabolic traits) regression models were used; cohort-specific results were combined in the meta-analysis and adjusted for multiple comparisons. (3) Results: Higher baseline BCAAs were associated with higher odds of prevalent T2D (OR1SD BCAA score = 1.46, 95% CI: 1.34-1.59, p < 0.0001) and higher risk of incident T2D (IRR1SD BCAA score = 1.24, 95% CI: 1.13-1.37, p < 0.0001). In multivariable longitudinal analysis, higher leucine and valine concentrations were associated with 2-year increase in insulin (beta 1SD leucine = 0.37 mcU/mL, 95% CI: 0.11-0.63, p < 0.05; beta 1SD valine = 0.43 mcU/mL, 95% CI: 0.17-0.68, p < 0.01). Tyrosine was a significant predictor of incident T2D (IRR = 1.31, 95% CI: 1.09-1.58, p < 0.05), as well as 2 year increases in HOMA-IR (beta 1SD tyrosine = 0.13, 95% CI: 0.04-0.22, p < 0.05) and insulin concentrations (beta 1SD tyrosine = 0.37 mcU/mL, 95% CI: 0.12-0.61, p < 0.05). (4) Conclusions: Our results confirmed the associations between BCAAs and prevalent and incident T2D, as well as concurrent measures of glycemia, dyslipidemia, and obesity, previously reported in predominantly White and Asian populations. Baseline leucine, valine, and tyrosine were predictors of 2 year increases in insulin, whereas tyrosine was a significant predictor of deteriorating insulin resistance over time. Our study suggests that BCAAs and tyrosine could serve as early markers of future glycemic changes in Puerto Ricans.
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Aminoácidos Aromáticos , Aminoácidos de Cadeia Ramificada , Fatores de Risco Cardiometabólico , Diabetes Mellitus Tipo 2 , Hispânico ou Latino , Humanos , Diabetes Mellitus Tipo 2/epidemiologia , Diabetes Mellitus Tipo 2/sangue , Feminino , Masculino , Pessoa de Meia-Idade , Aminoácidos de Cadeia Ramificada/sangue , Aminoácidos Aromáticos/sangue , Adulto , Hispânico ou Latino/estatística & dados numéricos , Estudos Longitudinais , Porto Rico/epidemiologia , Porto Rico/etnologia , Idoso , Prevalência , Boston/epidemiologia , Incidência , Obesidade/epidemiologia , Obesidade/etnologiaRESUMO
The influence of the geographical location on the chemical composition of commercial Sauvignon Blanc wines was investigated. The assay was carried out on Sauvignon Blanc wines from three cold-climate valleys in Central Chile, Casablanca, Leyda, and San Antonio. The analyses revealed clear variations in some chemical parameters, especially in titratable acidity, which was higher in the geographical areas closest to the Pacific Ocean, such as the Leyda and San Antonio valleys. Regarding the composition of low-molecular-weight phenolic compounds, 17 compounds were found, and the results show that the Casablanca valley exhibits a greater abundance of monomeric flavanols, such as (+)-catechin, whereas the Leyda valley shows a higher abundance in flavonols and phenolic acids esterified with tartaric acid. Concerning the aromatic compound profile, the wines from the Casablanca valley showed a greater abundance of esters, C13 norisoprenoids, and some terpenes. The PLS-DA analysis revealed some differences, especially between wines from Casablanca and Leyda, demonstrating that the difference in the chemical composition of the wines was influenced by the geographical area.
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In 2019, there was an environmental catastrophe in Brazil, when more than 5000 tons of unknown origin crude oil invaded beaches and mangroves. Two years later, two monitoring areas were selected to study seahorses' offspring: Massangana River estuary (apparently healthy area) and Cocaia Island (affected area). Thirty-six reproductive events of Hippocampus reidi (Syngnathidae) couples from these two areas were monitored to analyze the offspring. At the apparently healthy area, no newborns with malformations were found. However, the offspring from Cocaia Island showed a mean of 19.73% (±5.23) malformations in newborns. It is argued that the toxic/teratogenic effects of polycyclic aromatic hydrocarbons have affected the population in two ways: directly through the induction of mutations in the germ cells of the species and through a drastic reduction of the population (bottleneck effect) whose density observed today recovered through consanguineous couplings, potentiating deleterious genotypes in the offspring. Environ Toxicol Chem 2024;43:1996-2004. © 2024 SETAC.
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Poluição por Petróleo , Smegmamorpha , Poluentes Químicos da Água , Animais , Brasil , Poluentes Químicos da Água/toxicidade , Masculino , Feminino , Hidrocarbonetos Policíclicos Aromáticos/toxicidade , Monitoramento AmbientalRESUMO
This study assessed the effects of pollutants on Magallana gigas along a coastal zone with different levels of human activity: a highly impacted zone in the Bahía Blanca Estuary and a less impacted zone on the adjacent sandy beaches. Oysters collected in 2021 were analyzed for various factors, including metals, polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides, microplastics, oxidative stress and histology. Oysters of both environments exhibited detectable concentrations of all these pollutants in their tissues. However, the estuarine oysters showed higher concentrations of Zn, Cu and As and total PAHs than the beach oysters. Banned organochlorine pesticides were detected only in beach oysters. Estuarine oysters displayed morphological changes in their digestive gland including a reduction in the mean epithelial thickness of the tubule and elevated lipid peroxidation levels, indicating cellular damage. This study underscores the widespread presence of pollutants in M. gigas, indicating the need for effective strategies to safeguard coastal ecosystem health.
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Monitoramento Ambiental , Estuários , Ostreidae , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Animais , Poluentes Químicos da Água/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Argentina , Hidrocarbonetos Clorados/análise , Microplásticos/análise , Praguicidas/análise , Metais/análise , PraiasRESUMO
Polycyclic aromatic compounds (PACs) encompass a wide variety of organic analytes that have mutagenic and carcinogenic potentials for human health and are recalcitrant in the environment. Evaluating PACs levels in fuel (e.g., gasoline and diesel), food (e.g., grilled meat, fish, powdered milk, fruits, honey, and coffee) and environmental (e.g., industrial effluents, water, wastewater and marine organisms) samples are critical to determine the risk that these chemicals pose. Deep eutectic solvents (DES) have garnered significant attention in recent years as a green alternative to traditional organic solvents employed in sample preparation. DES are biodegradable, have low toxicities, ease of synthesis, low cost, and a remarkable ability to extract PACs. However, no comprehensive assessment of the use of DESs for extracting PACs from fuel, food and environmental samples has been performed. This review focused on research involving the utilization of DESs to extract PACs in matrices such as PAHs in environmental samples, NSO-HET in fuels, and bisphenols in foods. Chromatographic methods, such as gas chromatography (GC) and high-performance liquid chromatography (HPLC), were also revised, considering the sensibility to quantify these compound types. In addition, the characteristics of DES and advantages and limitations for PACs in the context of green analytical chemistry principles (GAC) and green profile based on metrics provide perspective and directions for future development.
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Solventes Eutéticos Profundos , Hidrocarbonetos Policíclicos Aromáticos , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/isolamento & purificação , Hidrocarbonetos Policíclicos Aromáticos/química , Solventes Eutéticos Profundos/química , Análise de Alimentos/métodos , Contaminação de Alimentos/análiseRESUMO
The study investigated the behavior of seventeen amino acids during spontaneous (SF) and starter culture (SC) fermentation of Criollo cocoa beans from Copallín, Guadalupe and Tolopampa, Amazonas-Peru. For this purpose, liquid chromatography (UHPLC) was used to quantify amino acids. Multivariate analysis was used to differentiate the phases of the fermentation process. The percentage of essential amino acids during SC fermentation (63.4%) was higher than SF (61.8%); it was observed that the starter culture accelerated their presence and increased their concentration during the fermentation process. The multivariate analysis identified a first stage (day 0 to day 2), characterized by a low content of amino acids that increased due to protein hydrolysis. The study showed that adding the starter culture (Saccharomyces cerevisiae) to the fermentation mass increased the concentration of essential amino acids (63.0%) compared to the spontaneous process (61.8%). Moreover, this addition reduced the fermentation time (3-4 days less), demonstrating that the fermentation process with a starter culture allows obtaining a better profile of amino acids precursors of flavor and aroma.
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Oceanic oil spills present significant ecological risks that have the potential to contaminate extensive areas, including coastal regions. The occurrence of the 2019 oil spill event in Brazil resulted in over 3000 km of contaminated beaches and shorelines. While assessing the impact on benthic and beach ecosystems is relatively straightforward due to direct accessibility, evaluating the ecotoxicological effects of open ocean oil spills on the pelagic community is a complex task. Difficulties are associated with the logistical challenges of responding promptly and, in case of the Brazilian mysterious oil spill, to the subsurface propagation of the oil that impeded remote visual detection. An oceanographic expedition was conducted in order to detect and evaluate the impact of this oil spill event along the north-eastern Brazilian continental shelf. The pursuit of dissolved and dispersed oil compounds was accomplished by standard oceanographic methods including seawater polycyclic aromatic hydrocarbons (PAHs) analysis, biomass stable carbon isotope (δ13C), particulate organic carbon to particulate organic nitrogen (POC:PON) ratios, nutrient analysis and ecotoxicological bioassays using the naupliar phase of the copepod Tisbe biminiensis. Significant ecotoxicological effects, reducing naupliar development by 20-40 %, were indicated to be caused by the presence of dispersed oil in the open ocean. The heterogeneous distribution of oil droplets aggravated the direct detection and biochemical indicators for oil are presented and discussed. Our findings serve as a case study for identifying and tracing subsurface propagation of oil, demonstrating the feasibility of utilizing standard oceanographic and ecotoxicological methods to assess the impacts of oil spill events in the open ocean. Ultimately, it encourages the establishment of appropriate measures and responses regarding the liability and regulation of entities to be held accountable for oil spills in the marine environment.
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Ecotoxicologia , Monitoramento Ambiental , Poluição por Petróleo , Hidrocarbonetos Policíclicos Aromáticos , Água do Mar , Poluentes Químicos da Água , Brasil , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade , Monitoramento Ambiental/métodos , Ecotoxicologia/métodos , Animais , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/toxicidade , Água do Mar/química , Copépodes/efeitos dos fármacos , EcossistemaRESUMO
Seven new abietane diterpenoids, comprising medusanthol A-G (1-3, 5, 7-9) and two previously identified analogs (4 and 6), were isolated from the hexane extract of the aerial parts of Medusantha martiusii. The structures of the compounds were elucidated by HRESIMS, 1D/2D NMR spectroscopic data, IR spectroscopy, NMR calculations with DP4+ probability analysis, and ECD calculations. The anti-neuroinflammatory potential of compounds 1-7 was evaluated by determining their ability to inhibit the production of nitric oxide (NO) and the proinflammatory cytokine TNF-α in BV2 microglia stimulated with LPS and IFN-γ. Compounds 1-4 and 7 exhibited decreased NO levels at a concentration of 12.5 µM. Compound 1 demonstrated strong activity with an IC50 of 3.12 µM, and compound 2 had an IC50 of 15.53 µM; both compounds effectively reduced NO levels compared to the positive control quercetin (IC50 11.8 µM). Additionally, both compounds significantly decreased TNF-α levels, indicating their potential as promising anti-neuroinflammatory agents.
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Abietanos , Anti-Inflamatórios , Microglia , Óxido Nítrico , Abietanos/farmacologia , Abietanos/química , Abietanos/isolamento & purificação , Anti-Inflamatórios/farmacologia , Anti-Inflamatórios/química , Animais , Óxido Nítrico/metabolismo , Camundongos , Microglia/efeitos dos fármacos , Microglia/metabolismo , Fator de Necrose Tumoral alfa/metabolismo , Extratos Vegetais/farmacologia , Extratos Vegetais/química , Linhagem Celular , Estrutura Molecular , Lipopolissacarídeos , Componentes Aéreos da Planta/químicaRESUMO
Ecuador is one of the world's leading producers of cacao beans, and Nacional x Trinitario cacao represents one of the most distinctive varieties due to its flavor and aroma characteristics. This study aimed to evaluate the effect of the starter culture isolated from microbial diversity during the spontaneous fermentation of Nacional x Trinitario cacao. A total of 249 microbial isolates were obtained from spontaneous culture, with Lactiplantibacillus (45 %), Saccharomyces (17 %), and Acetobacter (2 %) being the most relevant genera for fermentation. Tolerance tests were conducted to select microorganisms for the starter culture. Lactiplantibacillus plantarum exhibited the highest tolerance at pH 5 and 6 % ethanol and tolerated concentrations up to 15 % for glucose and fructose. Acetobacter pasteurianus grew at pH 2 and 6 % ethanol, tolerating high sugar concentrations of up to 15 % for glucose and 30 % for fructose, with growth observed in concentrations up to 5 % for lactic and acetic acid. Subsequently, a laboratory-scale fermentation was conducted with the formulated starter culture (SC) comprising S. cerevisiae, L. plantarum, and A. pasteurianus, which exhibited high tolerance to various stress conditions. The fermentation increased alcoholic compounds, including citrusy, fruity aromas, and floral notes such as 2-heptanol and phenylethyl alcohol, respectively 1.6-fold and 5.6-fold compared to the control. Moreover, the abundance of ketones 2-heptanone and 2-nonanone increased significantly, providing sweet green herbs and fruity woody aromas. Cacao fermented with this SC significantly enhanced the favorable aroma-producing metabolites characteristic of Fine-aroma cacao. These findings underscore the potential of tailored fermentation strategies to improve cacao product quality and sensory attributes, emphasizing the importance of ongoing research in optimizing fermentation processes for the cacao industry.
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In 2019, one of Brazil's most significant environmental disasters occurred, involving an oil spill that directly affected Pernambuco state. Contamination along the coast was evaluated by the quantification of polycyclic aromatic hydrocarbons (PAHs) in fifty seawater samples collected in the summer and winter of 2021. Analysis using fluorescence spectroscopy revealed that for all the samples, levels of dissolved/dispersed petroleum hydrocarbons (DDPHs) were higher than the regional baseline for tropical western shores of the Atlantic Ocean. GC-MS analyses quantified 17 PAHs in the samples, with highest total PAHs concentrations of 234 ng L-1 in summer and 33.3 ng L-1 in winter, which were consistent with the highest risks observed in ecotoxicity assays. The use of diagnostic ratios showed that the coast was impacted by a mixture of PAHs from petrogenic and pyrolytic sources. The results indicated the need for continuous monitoring of the regions affected by the 2019 spill.
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Monitoramento Ambiental , Poluição por Petróleo , Hidrocarbonetos Policíclicos Aromáticos , Água do Mar , Poluentes Químicos da Água , Hidrocarbonetos Policíclicos Aromáticos/análise , Brasil , Água do Mar/química , Poluentes Químicos da Água/análise , Petróleo/análise , Oceano Atlântico , Cromatografia Gasosa-Espectrometria de MassasRESUMO
Polycyclic aromatic hydrocarbons (PAHs) are organic compounds ubiquitous in the environment and known for their toxic, mutagenic, and carcinogenic effects. These compounds can bioaccumulate in the biota and be transferred through trophic webs. The franciscana dolphin (Pontoporia blainvillei), as top predators, can be an environmental sentinels. Thus, this study aimed to provide data about PAHs concentration in their hepatic tissue collected on the coast of Espírito Santo (Franciscana Management Area, FMA Ia), Rio de Janeiro (FMA IIa), and São Paulo states (FMA IIb), in Southeastern Brazil. PAHs were detected in 86 % of franciscana dolphins (n = 50). The highest ∑PAHsTotal median concentration was reported in FMA Ia followed by FMA IIb and FMA IIa (1055.6; 523.9, and 72.1 ng.g-1 lipid weight, respectively). Phenanthrene was detected in one fetus and two neonates, showing maternal transfer of PAHs in these dolphins. Evaluating PAHs with potential toxic effects is of utmost importance for the conservation of a threatened species.
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Golfinhos , Monitoramento Ambiental , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Animais , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/metabolismo , Golfinhos/metabolismo , Oceano Atlântico , Brasil , FemininoRESUMO
Polycyclic aromatic hydrocarbons (PAHs) are molecules with two or more fused aromatic rings that occur naturally in the environment due to incomplete combustion of organic substances. However, the increased demand for fossil fuels in recent years has increased anthropogenic activity, contributing to the environmental concentration of PAHs. The enzyme chlorocatechol 1,2-dioxygenase from Pseudomonas putida (Pp 1,2-CCD) is responsible for the breakdown of the aromatic ring of catechol, making it a potential player in bioremediation strategies. Pp 1,2-CCD can tolerate a broader range of substrates, including halogenated compounds, than other dioxygenases. Here, we report the construction of a chimera protein able to form biomolecular condensates with potential application in bioremediation. The chimera protein was built by conjugating Pp 1,2-CCD to low complex domains (LCDs) derived from the DEAD-box protein Dhh1. We showed that the chimera could undergo liquid-liquid phase separation (LLPS), forming a protein-rich liquid droplet under different conditions (variable protein and PEG8000 concentrations and pH values), in which the protein maintained its structure and main biophysical properties. The condensates were active against 4-chlorocatechol, showing that the chimera droplets preserved the enzymatic activity of the native protein. Therefore, it constitutes a prototype of a microreactor with potential use in bioremediation.
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Biodegradação Ambiental , Dioxigenases , Hidrocarbonetos Policíclicos Aromáticos , Dioxigenases/metabolismo , Dioxigenases/química , Hidrocarbonetos Policíclicos Aromáticos/química , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Pseudomonas putida/enzimologia , Catecóis/metabolismo , Catecóis/química , Proteínas de Bactérias/química , Proteínas de Bactérias/metabolismoRESUMO
This study conducted in Sergipe State, Brazil, aimed to investigate the presence of polycyclic aromatic hydrocarbons (PAHs) in the surface water of five rivers, determining their sources, spatial and temporal variations, and ecotoxicological risks. Correlation and principal component analyses were utilized to identify the relationship between PAH concentrations and water sample properties. Results indicated higher PAH concentrations during the rainy season, attributed to increased run-off and sediment resuspension. The composition of PAHs suggested a main petroleum source with organic material combustion in minor scale. Ecological risk assessment revealed potential risks to the ecosystem, emphasizing the need for continuous monitoring of PAHs pollution. This study highlights the importance of understanding and mitigating PAHs contamination in rivers to protect aquatic ecosystems.
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Monitoramento Ambiental , Hidrocarbonetos Policíclicos Aromáticos , Rios , Poluentes Químicos da Água , Hidrocarbonetos Policíclicos Aromáticos/análise , Brasil , Poluentes Químicos da Água/análise , Rios/química , Medição de Risco , Ecotoxicologia , Estações do Ano , EcossistemaRESUMO
Lippia alba (Mill.) N.E. Brown (Verbenaceae), popularly known as "erva cidreira", is one of the most used plants in Brazilian folk medicine. The species has several chemotypes and its volatile constituents have already been characterized, and present different chemical markers with known pharmacological properties, such as analgesic, sedative and antifungal properties. The objective of this study was to evaluate the anticholinesterase activity (AChE) of the essential oil of three chemotypes of Lippia alba and, by using molecular anchoring, determine the best receptor-ligand interaction energies of the main constituents present in the samples of oil. The essential oils were obtained via hydrodistillation (LA1 and LA2) and steam drag (LA3), and their volatile constituents determined using GC-MS. For the determination of anticholinesterase activity, direct bioautography and colorimetry assays based on Ellman's method were used. Molecular docking was performed using a multiple solution genetic algorithm and Merck molecular force field 94 (MMFF94) as the scoring function. In the main constituents of the oil samples, three chemotypes were identified for L. alba: LA1 is rich in citral, LA2 is rich in carvone and LA3 is rich in linalool. All L. alba chemotypes showed AChE enzyme inhibition with an IC50 of 3.57 µg/mL (LA1), 0.1 µg/mL (LA2) and 4.34 µg/mL (LA3). The molecular docking study complemented the results of the experiment and demonstrated significant interactions between the main constituents of the oils and the amino acid residues of the AChE enzyme. Irrespective of the chemotype, Lippia alba presents biotechnological potential for the discovery of anticholinesterase substances, with the chemotype LA2 (rich in carvone) being the most active.
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BACKGROUND: Although Basidiomycota produce pharmaceutically and ecologically relevant natural products, knowledge of how they coordinate their primary and secondary metabolism is virtually non-existent. Upon transition from vegetative mycelium to carpophore formation, mushrooms of the genus Psilocybe use L-tryptophan to supply the biosynthesis of the psychedelic tryptamine alkaloid psilocybin with the scaffold, leading to a strongly increased demand for this particular amino acid as this alkaloid may account for up to 2% of the dry mass. Using Psilocybe mexicana as our model and relying on genetic, transcriptomic, and biochemical methods, this study investigated if L-tryptophan biosynthesis and degradation in P. mexicana correlate with natural product formation. RESULTS: A comparative transcriptomic approach of gene expression in P. mexicana psilocybin non-producing vegetative mycelium versus producing carpophores identified the upregulation of L-tryptophan biosynthesis genes. The shikimate pathway genes trpE1, trpD, and trpB (encoding anthranilate synthase, anthranilate phosphoribosyltransferase, and L-tryptophan synthase, respectively) were upregulated in carpophores. In contrast, genes idoA and iasA, encoding indole-2,3-dioxygenase and indole-3-acetaldehyde synthase, i.e., gateway enzymes for L-tryptophan-consuming pathways, were massively downregulated. Subsequently, IasA was heterologously produced in Escherichia coli and biochemically characterized in vitro. This enzyme represents the first characterized microbial L-tryptophan-preferring acetaldehyde synthase. A comparison of transcriptomic data collected in this study with prior data of Psilocybe cubensis showed species-specific differences in how L-tryptophan metabolism genes are regulated, despite the close taxonomic relationship. CONCLUSIONS: The upregulated L-tryptophan biosynthesis genes and, oppositely, the concomitant downregulated genes encoding L-tryptophan-consuming enzymes reflect a well-adjusted cellular system to route this amino acid toward psilocybin production. Our study has pilot character beyond the genus Psilocybe and provides, for the first time, insight in the coordination of mushroom primary and secondary metabolism.
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This study comprehensively analyzes the magnetically induced current density of polycyclic compounds labeled as "aromatic chameleons" since they can arrange their π-electrons to exhibit aromaticity in both the ground and the lowest triplet state. These compounds comprise benzenoid moieties fused to a central skeleton with 4n π-electrons and traditional magnetic descriptors are biased due to the superposition of local magnetic responses. In the S0 state, our analysis reveals that the molecular constituent fragments preserve their (anti)aromatic features in agreement with two types of resonant structures: one associated with aromatic benzenoids and the other with a central antiaromatic ring. Regarding the T1 state, a global and diatropic ring current is revealed. Our aromaticity study is complemented with advanced electronic and geometric descriptors to consider different aspects of aromaticity, particularly important in the evaluation of excited state aromaticity. Remarkably, these descriptors consistently align with the general features on the main delocalization pathways in polycyclic hydrocarbons consisting of fused 4n π-electron rings. Moreover, our study demonstrates an inverse correlation between the singlet-triplet energy difference and the antiaromatic character of the central ring in S0.
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Many biogeochemical processes are modulated by dissolved organic matter (DOM), but the drivers influencing the chemodiversity of DOM compounds in Amazonian soils are poorly understood. It has also been theorized whether deforestation controls the decline of DOM. In this study, we collected soil samples from thirty sites across different regions of Brazil's Legal Amazon, and we investigated the trade-offs among soil physical-chemical properties and DOM chemodiversity. We employed optical spectroscopy, Fourier transform ion cyclotron resonance, and multivariate analysis. Our results indicated that, despite variations in land use and soil physical-chemical properties, factors such as the deforested site, geometric mean diameter, weighted average diameter, and soil organic carbon were the main influencers of DOM chemodiversity variation. These findings highlight the importance of considering DOM chemodiversity as closely related to land use and its potential use in developing deforestation models for predicting soil quality decline in Brazil's Legal Amazon.
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Due to its characteristic aroma and diverse therapeutic properties, lemongrass essential oil (LEO) has garnered increased attention in the pharmaceutical, food, and cosmetic industries. However, LEO's volatile nature, low chemical stability, and limited solubility in water limits its applications in the industry. Micro- and nanoencapsulation technologies emerge as a promising solution to overcome these challenges. A systematic methodology involving keyword searches in databases was employed to gather relevant literature on LEO micro- and nanoencapsulation, providing an extensive overview of techniques, processes, encapsulating materials, and possible applications. Beyond established methods, emerging techniques were explored. This review highlights the critical role of encapsulation in enhancing the thermal and chemical stability, applicability, bioavailability, and controlled release of LEO.
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Composição de Medicamentos , Óleos Voláteis , Óleos de Plantas , Óleos Voláteis/química , Óleos Voláteis/farmacologia , Óleos de Plantas/química , Humanos , Solubilidade , Estabilidade de Medicamentos , Disponibilidade Biológica , TerpenosRESUMO
OBJECTIVE: To measure dietary and urinary changes in sodium (Na) intake and excretion through the implementation of family gardens with aromatic herbs and workshops for cooking, using the herbs as a substitute for salt and seasoning powder. METHODS: Thirty-five participants from a neighborhood of Mexico City were included. A general questionnaire was administered to collect information on sociodemographic factors. At baseline and 3 months later, a dietary evaluation was conducted, and 24-hour urine samples were collected. Food items reported were classified according to the NOVA classification. Visits to participants´ houses were conducted to measure the amount of salt and seasoning powder added to food during the preparation of meals as well as a home food inventory. All participants were given a family garden with 6 aromatic herbs and a recipe book. The intervention included 7 cooking and 3 garden care workshops. Qualitative information on the experience was also collected. Linear regression models were run in order to estimate the contribution of each NOVA group, salt, and seasoning powder to total dietary Na intake. RESULTS: Participants were 44 years old on average and were mainly women (91.4%). The participation compliance in the workshops was 69.5%. After 3 months, there was a Na intake mean reduction of 976 mg. There was also a reduction in the excreted urinary Na of 325 mg per day. CONCLUSION: A positive level of involvement in this program had a direct influence on dietary habits to lower Na consumption.