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Chemosphere Jun 2024A comprehensive kinetic model has been developed to address the factors and processes governing the photocatalytic removal of gaseous ethanol by using ZnO loaded in a...
A comprehensive kinetic model has been developed to address the factors and processes governing the photocatalytic removal of gaseous ethanol by using ZnO loaded in a prototype air purifier. This model simultaneously tracks the concentrations of ethanol and acetaldehyde (as its primary oxidation product) in both gas phase and on the catalyst surface. It accounts for reversible adsorption of both compounds to assign kinetic reaction parameters for different degradation pathways. The effects of oxygen vacancies on the catalyst have been validated through the comparative assessment on the catalytic performance of commercial ZnO before and after the reduction pre-treatment (10% H/Ar gas at 500 °C). The influence of humidity has also been assessed by partitioning the concentrations of water molecules across the gas phase and catalyst surface interface. Given the significant impact of adsorption on photocatalytic processes, the beginning phases of all experiments (15 min in the dark) are integrated into the model. Results showcase a notable decrease in the adsorption removal of ethanol and acetaldehyde with an increase in relative humidity from 5% to 75%. The estimated number of active sites, as determined by the model, increases from 7.34 10 in commercial ZnO to 8.86 10 mol g in reduced ZnO. Furthermore, the model predicts that the reaction occurs predominantly on the catalyst surface while only 14% in the gas phase. By using quantum yield calculations, the optimal humidity level for photocatalytic degradation is identified as 25% with the highest quantum yield of 6.98 10 (commercial ZnO) and 10.41 10 molecules photon (reduced ZnO) catalysts.
Topics: Zinc Oxide; Acetaldehyde; Kinetics; Ethanol; Catalysis; Humidity; Oxygen; Adsorption; Air Pollutants; Oxidation-Reduction; Models, Chemical
PubMed: 38677616
DOI: 10.1016/j.chemosphere.2024.142118 -
Plants (Basel, Switzerland) Apr 2024Volatile organic compounds (VOCs) emitted by plants may help in understanding the status of a plant's physiology and its coping with mild to severe stress. Future...
Volatile organic compounds (VOCs) emitted by plants may help in understanding the status of a plant's physiology and its coping with mild to severe stress. Future climatic projections reveal that shifts in temperature and CO availability will occur, and plants may incur the uncoupling of carbon assimilation and synthesis of key molecules. This study explores the patterns of emissions of key VOCs (isoprene, methanol, acetaldehyde, and acetic acid) emitted by poplar leaves (more than 350) under a combined gradient of temperature (12-42 °C) and air CO concentration (400-1500 ppm), along with measurements of photosynthetic rates and stomatal conductance. Isoprene emission exhibited a rise with temperature and CO availability, peaking at 39 °C, the temperature at which methanol emission started to peak, illustrating the limit of stress tolerance to severe damage. Isoprene emission was uncoupled from the photosynthesis rate, indicating a shift from the carbon source for isoprene synthesis, while assimilation was decreased. Methanol and acetaldehyde emissions were correlated with stomatal conductance and peaked at 25 °C and 1200 ppm CO. Acetic acid emissions lacked a clear correlation with stomatal conductance and the emission pattern of its precursor acetaldehyde. This study offers crucial insights into the limitations of photosynthetic carbon and stress tolerance.
PubMed: 38674574
DOI: 10.3390/plants13081165 -
Environmental Science and Pollution... May 2024Emissions of volatile organic compounds (VOCs) in vehicles represent a significant problem, causing unpleasant odors. To mitigate VOCs and odors in vehicles, it is...
Emissions of volatile organic compounds (VOCs) in vehicles represent a significant problem, causing unpleasant odors. To mitigate VOCs and odors in vehicles, it is critical to choose interior parts with low odor and VOC emissions. However, prevailing odor evaluation methods are subjective, costly, and potentially harmful to the health of evaluators. In this study, we analyzed 139 automotive interior parts and 92 vehicles, establishing a cost-effective, data-driven method for odor evaluation. The contents of benzene, toluene, ethylbenzene, xylene, styrene, formaldehyde, acetaldehyde, acrolein, and total volatile organic compounds (TVOC) were detected by thermal desorption gas chromatography-mass spectrometry (TD-GC/MS) and high-performance liquid chromatography with an ultraviolet detector (HPLC-UV). Professional odor evaluators assessed the odors, identifying intensity levels from 2.0 to 4.5 in interior parts and 2.5 to 3.5 in whole vehicles. Leveraging this data, we applied four supervised learning algorithms to develop predictive models for the odor intensity of both interior parts and entire vehicles. During model training, we implemented early stopping techniques for the artificial neural network (ANN) and convolutional neural network-bidirectional long short-term memory (CNN-BiLSTM) models, while optimizing the support vector machine (SVM) and extreme gradient boosting (XGBoost) models using the GridSearch algorithm. The evaluation results reveal that the CNN-BiLSTM model performs the best, achieving an average accuracy of 89% for unknown samples within an odor intensity level of 0.5. The root mean square error (RMSE) is 0.24, and the mean absolute error (MAE) is 0.08. The model also underwent a sevenfold cross-validation, achieving an accuracy of 83.43%. Additionally, we employed SHapley Additive exPlanations (SHAP) for the interpretative analysis of the model, which confirmed the consistency of each VOC's odor contribution with human olfactory rules. By predicting odors based on VOCs through supervised learning, this study reduces the costs and enhances the efficiency and applicability of odor assessment across various vehicle interiors.
Topics: Odorants; Volatile Organic Compounds; Neural Networks, Computer; Gas Chromatography-Mass Spectrometry; Vehicle Emissions; Support Vector Machine
PubMed: 38668943
DOI: 10.1007/s11356-024-33293-y -
Toxics Mar 2024In recent years, commercial air transport has increased considerably. However, the compositions and source profiles of volatile organic compounds (VOCs) emitted from...
In recent years, commercial air transport has increased considerably. However, the compositions and source profiles of volatile organic compounds (VOCs) emitted from aircraft are still not clear. In this study, the characteristics of VOCs (including oxygenated VOCs (OVOCs)) emitted from airport sources were measured at Shenzhen Bao'an International Airport. The results showed that the compositions and proportions of VOC species showed significant differences as the aircraft operating state changed. OVOCs were the dominant species and accounted for 63.17%, 58.44%, and 51.60% of the total VOC mass concentration during the taxiing, approach, and take-off stages. Propionaldehyde and acetone were the main OVOCs, and dichloromethane and 1,2-dichloroethane were the main halohydrocarbons. Propane had the highest proportion among all alkanes, while toluene and benzene were the predominant aromatic hydrocarbons. Compared with the source profiles of VOCs from construction machinery, the proportions of halogenated hydrocarbons and alkanes emitted from aircraft were significantly higher, as were those of propionaldehyde and acetone. OVOCs were still the dominant VOC species in aircraft emissions, and their calculated ozone formation potential (OFP) was much higher than that of other VOC species at all stages of aircraft operations. Acetone, propionaldehyde, formaldehyde, acetaldehyde, and ethylene were the greatest contributors to ozone production. This study comprehensively measured the distribution characteristics of VOCs, and its results will aid in the construction of a source profile inventory of VOCs emitted from aircraft sources in real atmospheric environments.
PubMed: 38668466
DOI: 10.3390/toxics12040243 -
Membranes Apr 2024Pervaporation is a membrane-based process used for the separation of liquid mixtures. As this membrane process is governed by the differences in the sorption and...
Pervaporation is a membrane-based process used for the separation of liquid mixtures. As this membrane process is governed by the differences in the sorption and diffusivities of separated components, close boiling mixtures and azeotropic mixtures can effectively be separated. The dehydration of ethanol is the most common application of hydrophilic pervaporation. The pilot scale properties of hydrophilic composite poly(vinyl alcohol) PVA membrane (PERVAP 2200) in contact with wet raw bioethanol are presented. The wet raw bioethanol was composed of ethanol (82.4-89.6 wt%), water (5.9-8.5 wt%), methanol (2.3-6.9 wt%), cyclohexane (0.2-2.4 wt%), higher alcohols (0.2-1.3 wt%), and acetaldehyde (0.004-0.030 wt%). All experiments were performed using a SULZER ECO-001 plant equipped with a 1.5 m membrane module. The efficiency of the dehydration process (i.e., membrane selectivity, permeate flux, degree of dehydration) was discussed as a function of the following parameters: the feed temperature, the feed composition, and the feed flow rate through the module. It was found that the low feed flow rate influenced the dehydration efficiency as the enthalpy of evaporation caused a high temperature drop in the module (around 25 °C at a feed flow rate equal to 5 kg h). The separation coefficient during pervaporation was in the range of 600-1200, depending on the feed composition. The increase in temperature augmented the permeation flux and shortened the time needed to reach the assumed level of dehydration. It was revealed that dehydration by pervaporation using ECO-001 pilot plant is an efficient process, allowing also to investigate the influence of various parameters on the process efficiency.
PubMed: 38668118
DOI: 10.3390/membranes14040090 -
Dalton Transactions (Cambridge, England... May 2024In this study, we performed the CO reduction reaction (CORR) using a structural composite catalyst of cuprous oxide (CuO) and silver (Ag) that was simultaneously...
In this study, we performed the CO reduction reaction (CORR) using a structural composite catalyst of cuprous oxide (CuO) and silver (Ag) that was simultaneously electrodeposited. While the underneath Ag electrodeposits maintained their spiky backbone structures even after the CORR, the CuO deposits were reduced to Cu(111) and relocated on the backbone template. The structural changes in CuO to Cu increase the active area of the Cu-Ag interface, resulting in a remarkable production rate of 125.01 μmol h of liquid C chemicals the stabilization of the C-C coupling of the key intermediate species of acetaldehyde. This study provides new insights into designing a bimetallic catalyst for producing sustainable C products from CO without any selectivity towards the production of methane.
PubMed: 38666327
DOI: 10.1039/d4dt00199k -
Fungal Biology and Biotechnology Apr 2024Although Basidiomycota produce pharmaceutically and ecologically relevant natural products, knowledge of how they coordinate their primary and secondary metabolism is...
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.
PubMed: 38664850
DOI: 10.1186/s40694-024-00173-6 -
Microbial Cell Factories Apr 2024Excessive alcohol consumption has been consistently linked to serious adverse health effects, particularly affecting the liver. One natural defense against the...
BACKGROUND
Excessive alcohol consumption has been consistently linked to serious adverse health effects, particularly affecting the liver. One natural defense against the detrimental impacts of alcohol is provided by alcohol dehydrogenase (ADH) and acetaldehyde dehydrogenase (ALDH), which detoxify harmful alcohol metabolites. Recent studies have shown that certain probiotic strains, notably Lactobacillus spp., possess alcohol resistance and can produce these critical enzymes. Incorporating these probiotics into alcoholic beverages represents a pioneering approach that can potentially mitigate the negative health effects of alcohol while meeting evolving consumer preferences for functional and health-centric products.
RESULTS
Five lactic acid bacteria (LAB) isolates were identified: Lactobacillus paracasei Alc1, Lacticaseibacillus rhamnosus AA, Pediococcus acidilactici Alc3, Lactobacillus paracasei Alc4, and Pediococcus acidilactici Alc5. Assessment of their alcohol tolerance, safety, adhesion ability, and immunomodulatory effects identified L. rhamnosus AA as the most promising alcohol-tolerant probiotic strain. This strain also showed high production of ADH and ALDH. Whole genome sequencing analysis revealed that the L. rhamnosus AA genome contained both the adh (encoding for ADH) and the adhE (encoding for ALDH) genes.
CONCLUSIONS
L. rhamnosus AA, a novel probiotic candidate, showed notable alcohol resistance and the capability to produce enzymes essential for alcohol metabolism. This strain is a highly promising candidate for integration into commercial alcoholic beverages upon completion of comprehensive safety and functionality evaluations.
Topics: Humans; Alcohol Dehydrogenase; Probiotics; Ethanol; Lactobacillus; Lactobacillales; Lacticaseibacillus rhamnosus; Aldehyde Oxidoreductases; Pediococcus acidilactici
PubMed: 38659044
DOI: 10.1186/s12934-024-02375-4 -
Methods in Enzymology 2024β-Hydroxy-α-amino acids (βHAAs) are an essential class of building blocks of therapeutically important compounds and complex natural products. They contain two chiral...
β-Hydroxy-α-amino acids (βHAAs) are an essential class of building blocks of therapeutically important compounds and complex natural products. They contain two chiral centers at Cα and Cβ positions, resulting in four possible diastereoisomers. Many innovative asymmetric syntheses have been developed to access structurally diverse βHAAs. The main challenge, however, is the control of the relative and absolute stereochemistry of the asymmetric carbons in a sustainable way. In this respect, there has been considerable attention focused on the chemoenzymatic synthesis of βHAAs via a one-step process. Nature has evolved different enzymatic routes to produce these valuable βHAAs. Among these naturally occurring transformations, L-threonine transaldolases present potential biocatalysts to generate βHAAs in situ. 4-Fluorothreonine transaldolase from Streptomyces sp. MA37 (FTaseMA) catalyzes the cross-over transaldolation reaction between L-Thr and fluoroacetaldehyde to give 4-fluorothreonine and acetaldehyde (Ad). It has been demonstrated that FTaseMA displays considerable substrate plasticity toward structurally diverse aldehyde acceptors, leading to the production of various βHAAs. In this chapter, we describe methods for the preparation of FTaseMA, and the chemoenzymatic synthesis of βHAAs from various aldehydes and L-Thr using FTaseMA.
Topics: Streptomyces; Transaldolase; Threonine; Biocatalysis; Amino Acids; Substrate Specificity; Acetaldehyde; Bacterial Proteins; Enzyme Assays; Stereoisomerism
PubMed: 38658079
DOI: 10.1016/bs.mie.2023.12.017 -
The Science of the Total Environment Jun 2024In the context of the increasing global use of ethanol biofuel, this work investigates the concentrations of ethanol, methanol, and acetaldehyde, in both the gaseous...
In the context of the increasing global use of ethanol biofuel, this work investigates the concentrations of ethanol, methanol, and acetaldehyde, in both the gaseous phase and rainwater, across six diverse urban regions and biomes in Brazil, a country where ethanol accounts for nearly half the light-duty vehicular fuel consumption. Atmospheric ethanol median concentrations in São Paulo (SP) (12.3 ± 12.1 ppbv) and Ribeirão Preto (RP) (12.1 ± 10.9 ppbv) were remarkably close, despite the SP vehicular fleet being ∼13 times larger. Likewise, the rainwater VWM ethanol concentration in SP (4.64 ± 0.38 μmol L) was only 26 % higher than in RP (3.42 ± 0.13 μmol L). This work demonstrated the importance of evaporative emissions, together with biomass burning, as sources of the compounds studied. The importance of biogenic emissions of methanol during forest flooding was identified in campaigns in the Amazon and Atlantic forests. Marine air masses arriving at a coastal site led to the lowest concentrations of ethanol measured in this work. Besides vehicular and biomass burning emissions, secondary formation of acetaldehyde by photochemical reactions may be relevant in urban and non-urban regions. The combined deposition flux of ethanol and methanol was 6.2 kg ha year, avoiding oxidation to the corresponding and more toxic aldehydes. Considering the species determined here, the ozone formation potential (OFP) in RP was around two-fold higher than in SP, further evidencing the importance of emissions from regional distilleries and biomass burning, in addition to vehicles. At the forest and coastal sites, the OFP was approximately 5 times lower than at the urban sites. Our work evidenced that transition from gasoline to ethanol or ethanol blends brings the associated risk of increasing the concentrations of highly toxic aldehydes and ozone, potentially impacting the atmosphere and threatening air quality and human health in urban areas.
Topics: Brazil; Acetaldehyde; Ethanol; Environmental Monitoring; Methanol; Rain; Air Pollutants; Cities
PubMed: 38649057
DOI: 10.1016/j.scitotenv.2024.172629