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1.
Plant Mol Biol ; 114(4): 86, 2024 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-39023668

RESUMO

Abiotic stress is a major factor affecting crop productivity. Chemical priming is a promising strategy to enhance tolerance to abiotic stress. In this study, we evaluated the use of 1-butanol as an effectual strategy to enhance drought stress tolerance in Arabidopsis thaliana. We first demonstrated that, among isopropanol, methanol, 1-butanol, and 2-butanol, pretreatment with 1-butanol was the most effective for enhancing drought tolerance. We tested the plants with a range of 1-butanol concentrations (0, 10, 20, 30, 40, and 50 mM) and further determined that 20 mM was the optimal concentration of 1-butanol that enhanced drought tolerance without compromising plant growth. Physiological tests showed that the enhancement of drought tolerance by 1-butanol pretreatment was associated with its stimulation of stomatal closure and improvement of leaf water retention. RNA-sequencing analysis revealed the differentially expressed genes (DEGs) between water- and 1-butanol-pretreated plants. The DEGs included genes involved in oxidative stress response processes. The DEGs identified here partially overlapped with those of ethanol-treated plants. Taken together, the results show that 1-butanol is a novel chemical priming agent that effectively enhances drought stress tolerance in Arabidopsis plants, and provide insights into the molecular mechanisms of alcohol-mediated abiotic stress tolerance.


Assuntos
1-Butanol , Arabidopsis , Secas , Regulação da Expressão Gênica de Plantas , Estresse Fisiológico , Arabidopsis/genética , Arabidopsis/efeitos dos fármacos , Arabidopsis/fisiologia , 1-Butanol/farmacologia , Regulação da Expressão Gênica de Plantas/efeitos dos fármacos , Estresse Fisiológico/efeitos dos fármacos , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/genética , Folhas de Planta/fisiologia , Água
2.
Ecotoxicol Environ Saf ; 272: 116055, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38340597

RESUMO

2-Methyl-1-butanol (2MB) and 3-Methyl-1-butanol (3MB) are microbial volatile organic compounds (VOCs) and found in indoor air. Here, we applied rice as a bioindicator to investigate the effects of these indoor microbial volatile pollutants. A remarkable decrease in germination percentage, shoot and root elongation, as well as lateral root numbers were observed in 3MB. Furthermore, ROS production increased by 2MB and 3MB, suggesting that pentanol isomers could induce cytotoxicity in rice seedlings. The enhancement of peroxidase (POD) and catalase (CAT) activity provided evidence that pentanol isomers activated the enzymatic antioxidant scavenging systems, with a more significant effect observed in 3MB. Furthermore, 3MB induced higher activity levels of glutathione (GSH), oxidized glutathione (GSSG), and the GSH/GSSG ratio in rice compared to the levels induced by 2MB. Additionally, qRT-PCR analysis showed more up-regulation in the expression of glutaredoxins (GRXs), peroxiredoxins (PRXs), thioredoxins (TRXs), and glutathione S-transferases (GSTUs) genes in 3MB. Taking the impacts of pentanol isomers together, the present study suggests that 3MB exhibits more cytotoxic than 2MB, as such has critical effects on germination and the early seedling stage of rice. Our results provide molecular insights into how isomeric indoor microbial volatile pollutants affect plant growth through airborne signals.


Assuntos
Poluentes Ambientais , Oryza , Antioxidantes/metabolismo , Plântula , Oryza/metabolismo , Pentanóis/metabolismo , Pentanóis/farmacologia , 1-Butanol/metabolismo , 1-Butanol/farmacologia , Poluentes Ambientais/metabolismo , Dissulfeto de Glutationa/metabolismo , Estresse Oxidativo , Glutationa/metabolismo , Raízes de Plantas/metabolismo
3.
J Korean Med Sci ; 38(19): e140, 2023 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-37191844

RESUMO

BACKGROUND: 4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) is known as a lung carcinogen. The objective of this study was to investigate associations of urine NNAL concentrations and smoking status. METHODS: This was a cross-sectionally designed study based on data from the 2016-2018 Korean National Health and Nutrition Examination Survey. A total of 2,845 participants were classified into past-smoker, electronic cigarette (e-cigar) only, dual-user, and cigarette only smoker groups. All sampling and weight variables were stratified and analysis was conducted accounting for the complex sampling design. Analysis of covariance was used to compare the geometric mean of urine NNAL concentrations and log-transformed urine NNAL level among smoking status with weighted survey design. Post hoc paired comparisons with Bonferroni adjustment was performed according to smoking status. RESULTS: The estimated geometric mean concentrations of urine NNAL were 1.974 ± 0.091, 14.349 ± 5.218, 89.002 ± 11.444, and 117.597 ± 5.459 pg/mL in past-smoker, e-cigar only, dual-user, and cigarette only smoker groups, respectively. After fully adjusting, log-transformed urine NNAL level was significantly different among groups (P < 0.001). Compared with the past-smoker group, e-cigar only, dual-user, and cigarette only smoker groups showed significantly higher log-transformed urine NNAL concentrations in post hoc test (all P < 0.05). CONCLUSION: E-cigar only, dual-user, and cigarette only smoker groups showed significantly higher geometric mean concentrations of urine NNAL than the past-smoker group. Conventional cigarette, dual users, and e-cigar users can potentially show harmful health effects from NNAL.


Assuntos
Sistemas Eletrônicos de Liberação de Nicotina , Nitrosaminas , Produtos do Tabaco , Humanos , Carcinógenos/análise , Fumar , Nitrosaminas/urina , Inquéritos Nutricionais
4.
Molecules ; 28(3)2023 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-36771177

RESUMO

The previous biodiesel purification by Solvent-Aided Crystallization (SAC) using 1-butanol as assisting agent and parameters for SAC were optimized such as coolant temperature, cooling time and stirring speed. Meanwhile, 2-Methyltetrahydrofuran (2-MeTHF) was selected as an alternative to previous organic solvents for this study. In this context, it is used to replace solvent 1-butanol from a conducted previous study. This study also focuses on the technological improvements in the purification of biodiesel via SAC as well as to produce an even higher purity of biodiesel. Experimental works on the transesterification process to produce crude biodiesel were performed and SAC was carried out to purify the crude biodiesel. The crude biodiesel content was analyzed by using Gas Chromatography-Mass Spectrometry (GC-MS) and Differential Scanning Calorimetry (DSC) to measure the composition of Fatty Acid Methyl Esters (FAME) present. The optimum value to yield the highest purity of FAME for parameters coolant temperature, cooling time, and stirring speed is -4 °C, 10 min and 210 rpm, respectively. It can be concluded that the assisting solvent 2-MeTHF has a significant effect on the process parameters to produce purified biodiesel according to the standard requirement.

5.
Molecules ; 28(12)2023 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-37375253

RESUMO

The present paper contains data on the density (ρ), sound velocity (u), and specific heat capacity cp of the mixture of N,N-dimethylformamide + 1-butanol (DMF + BuOH) determined in the entire concentration range of solution and in the temperature range (293.15-318.15) K. The analysis of thermodynamic functions such as isobaric molar expansion, isentropic and isothermal molar compression, isobaric and isochoric molar heat capacity, as well as their excess functions (Ep,mE,KS,mE,KT,mE,Cp, mE,CV, mE) and also VmE was undertaken. The analysis of changes in the physicochemical quantities was based on consideration of the system in terms of intermolecular interactions and resulting changes in the mixture structure. The results available in the literature were confusing during the analysis and became the reason for our decision to thoroughly examine the system. What is more, for a system whose components are widely used, there is very scarce information in the literature regarding the heat capacity of the tested mixture, which was also achieved and presented in this publication. The conclusions drawn from so many data points allow us to approximate and understand the changes that occur in the structure of the system due to the repeatability and consistency of the obtained results.

6.
Metab Eng ; 69: 87-97, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34774761

RESUMO

Cyanobacteria hold promise for renewable chemical production due to their photosynthetic nature, but engineered strains frequently display poor production characteristics. These difficulties likely arise in part due to the distinctive photoautotrophic metabolism of cyanobacteria. In this work, we apply a genome-scale metabolic model of the cyanobacteria Synechococus sp. PCC 7002 to identify strain designs accounting for this unique metabolism that are predicted to improve the production of various biofuel alcohols (e.g. 2-methyl-1-butanol, isobutanol, and 1-butanol) synthesized via an engineered biosynthesis pathway. Using the model, we identify that the introduction of a large, non-native NADH-demand into PCC 7002's metabolic network is predicted to enhance production of these alcohols by promoting NADH-generating reactions upstream of the production pathways. To test this, we construct strains of PCC 7002 that utilize a heterologous, NADH-dependent nitrite reductase in place of the native, ferredoxin-dependent enzyme to create an NADH-demand in the cells when grown on nitrate-containing media. We find that photosynthetic production of both isobutanol and 2-methyl-1-butanol is significantly improved in the engineered strain background relative to that in a wild-type background. We additionally identify that the use of high-nutrient media leads to a substantial prolongment of the production curve in our alcohol production strains. The metabolic engineering strategy identified and tested in this work presents a novel approach to engineer cyanobacterial production strains that takes advantage of a unique aspect of their metabolism and serves as a basis on which to further develop strains with improved production of these alcohols and related products.


Assuntos
Synechococcus , 1-Butanol/metabolismo , Butanóis , NAD/genética , NAD/metabolismo , Nitratos/metabolismo , Synechococcus/genética , Synechococcus/metabolismo
7.
Microb Cell Fact ; 21(1): 7, 2022 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-34991586

RESUMO

BACKGROUND: Cyanobacteria are engineered via heterologous biosynthetic pathways to produce value-added chemicals via photosynthesis. Various chemicals have been successfully produced in engineered cyanobacteria. Chemical inducer-dependent promoters are used to induce the expression of target biosynthetic pathway genes. A chemical inducer is not ideal for large-scale reactions owing to its high cost; therefore, it is important to develop scaling-up methods to avoid their use. In this study, we designed a green light-inducible alcohol production system using the CcaS/CcaR green light gene expression system in the cyanobacterium Synechocystis sp. PCC 6803 (PCC 6803). RESULTS: To establish the green light-inducible production of isobutanol and 3-methyl-1-butanol (3MB) in PCC 6803, keto-acid decarboxylase (kdc) and alcohol dehydrogenase (adh) were expressed under the control of the CcaS/CcaR system. Increases in the transcription level were induced by irradiation with red and green light without severe effects on host cell growth. We found that the production of isobutanol and 3MB from carbon dioxide (CO2) was induced under red and green light illumination and was substantially repressed under red light illumination alone. Finally, production titers of isobutanol and 3MB reached 238 mg L-1 and 75 mg L-1, respectively, in 5 days under red and green light illumination, and these values are comparable to those reported in previous studies using chemical inducers. CONCLUSION: A green light-induced alcohol production system was successfully integrated into cyanobacteria to produce value-added chemicals without using expensive chemical inducers. The green light-regulated production of isobutanol and 3MB from CO2 is eco-friendly and cost-effective. This study demonstrates that light regulation is a potential tool for producing chemicals and increases the feasibility of cyanobacterial bioprocesses.


Assuntos
Butanóis/metabolismo , Engenharia Metabólica , Pentanóis/metabolismo , Synechocystis/genética , Synechocystis/metabolismo , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Luz , Fotorreceptores Microbianos/genética , Fotorreceptores Microbianos/metabolismo , Fotossíntese , Regiões Promotoras Genéticas , Synechocystis/crescimento & desenvolvimento
8.
Molecules ; 27(23)2022 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-36500443

RESUMO

The ability to predict the behaviour of high-pressure mixtures of carbon dioxide and alcohol is important for industrial purposes. The equilibrium composition of three binary carbon dioxide-alcohol systems was measured at temperatures of 313.15 K and 333.15 K and at pressures of up to 100 bar for carbon dioxide-2-propanol, up to 160 bar for carbon dioxide-1-butanol and up to 150 bar for carbon dioxide-2-butanol. Different equilibrium compositions of carbon dioxide in alcohols were observed despite their similar molecular weight (M2-propanol = 60.100 g mol-1, M1-butanol = 74.121 g mol-1 and M2-butanol = 74.122 g mol-1) and place in the functional hydroxyl group (first or second carbon molecule). It is assumed that the differences in the phase equilibria are due to different vapor pressures, polarities and solute-solute interactions.


Assuntos
1-Butanol , 2-Propanol , Dióxido de Carbono , Etanol
9.
J Mol Cell Cardiol ; 152: 105-117, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33307092

RESUMO

Gut microbiome (GMB) has been increasingly recognized as a contributor to development and progression of heart failure (HF), immune-mediated subtypes of cardiomyopathy (myocarditis and anthracycline-induced cardiotoxicity), response to certain cardiovascular drugs, and HF-related comorbidities, such as chronic kidney disease, cardiorenal syndrome, insulin resistance, malnutrition, and cardiac cachexia. Gut microbiome is also responsible for the "gut hypothesis" of HF, which explains the adverse effects of gut barrier dysfunction and translocation of GMB on the progression of HF. Furthermore, accumulating evidence has suggested that gut microbial metabolites, including short chain fatty acids, trimethylamine N-oxide (TMAO), amino acid metabolites, and bile acids, are mechanistically linked to pathogenesis of HF, and could, therefore, serve as potential therapeutic targets for HF. Even though there are a variety of proposed therapeutic approaches, such as dietary modifications, prebiotics, probiotics, TMAO synthesis inhibitors, and fecal microbial transplant, targeting GMB in HF is still in its infancy and, indeed, requires further preclinical and clinical evidence. In this review, we aim to highlight the role gut microbiome plays in HF pathophysiology and its potential as a novel therapeutic target in HF.


Assuntos
Microbioma Gastrointestinal , Insuficiência Cardíaca/patologia , Animais , Comorbidade , Insuficiência Cardíaca/epidemiologia , Insuficiência Cardíaca/microbiologia , Humanos
10.
Appl Environ Microbiol ; 87(11)2021 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-33741627

RESUMO

Sulfolobus acidocaldarius is a thermoacidophilic crenarchaeon with optimal growth at 80°C and pH 2 to 3. Due to its unique physiological properties, allowing life at environmental extremes, and the recent availability of genetic tools, this extremophile has received increasing interest for biotechnological applications. In order to elucidate the potential of tolerating process-related stress conditions, we investigated the response of S. acidocaldarius toward the industrially relevant organic solvent 1-butanol. In response to butanol exposure, biofilm formation of S. acidocaldarius was enhanced and occurred at up to 1.5% (vol/vol) 1-butanol, while planktonic growth was observed at up to 1% (vol/vol) 1-butanol. Confocal laser-scanning microscopy revealed that biofilm architecture changed with the formation of denser and higher tower-like structures. Concomitantly, changes in the extracellular polymeric substances with enhanced carbohydrate and protein content were determined in 1-butanol-exposed biofilms. Using scanning electron microscopy, three different cell morphotypes were observed in response to 1-butanol. Transcriptome and proteome analyses were performed comparing the response of planktonic and biofilm cells in the absence and presence of 1-butanol. In response to 1% (vol/vol) 1-butanol, transcript levels of genes encoding motility and cell envelope structures, as well as membrane proteins, were reduced. Cell division and/or vesicle formation were upregulated. Furthermore, changes in immune and defense systems, as well as metabolism and general stress responses, were observed. Our findings show that the extreme lifestyle of S.acidocaldarius coincided with a high tolerance to organic solvents. This study provides what may be the first insights into biofilm formation and membrane/cell stress caused by organic solvents in S. acidocaldariusIMPORTANCEArchaea are unique in terms of metabolic and cellular processes, as well as the adaptation to extreme environments. In the past few years, the development of genetic systems and biochemical, genetic, and polyomics studies has provided deep insights into the physiology of some archaeal model organisms. In this study, we used S. acidocaldarius, which is adapted to the two extremes of low pH and high temperature, to study its tolerance and robustness as well as its global cellular response toward organic solvents, as exemplified by 1-butanol. We were able to identify biofilm formation as a primary cellular response to 1-butanol. Furthermore, the triggered cell/membrane stress led to significant changes in culture heterogeneity accompanied by changes in central cellular processes, such as cell division and cellular defense systems, thus suggesting a global response for the protection at the population level.


Assuntos
1-Butanol/efeitos adversos , Biofilmes/efeitos dos fármacos , Plâncton/efeitos dos fármacos , Proteoma , Solventes/efeitos adversos , Sulfolobus acidocaldarius/fisiologia , Transcriptoma , Aclimatação , Proteínas de Bactérias/metabolismo , Genes Bacterianos , Microscopia Eletrônica de Varredura , Plâncton/fisiologia , Estresse Fisiológico , Sulfolobus acidocaldarius/efeitos dos fármacos , Sulfolobus acidocaldarius/genética , Sulfolobus acidocaldarius/ultraestrutura
11.
Int J Legal Med ; 135(1): 223-233, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33026504

RESUMO

The objective of this study was to determine if a relationship between microbial neoformation of volatiles and the post-mortem interval (PMI) exists, and if the volatiles could be used as a tool to improve the precision of PMI estimation in decomposed human remains found in an indoor setting. Chromatograms from alcohol analysis (femoral vein blood) of 412 cases were retrospectively assessed for the presence of ethanol, N-propanol, 1-butanol, and acetaldehyde. The most common finding was acetaldehyde (83% of the cases), followed by ethanol (37%), N-propanol (21%), and 1-butanol (4%). A direct link between the volatiles and the PMI or the degree of decomposition was not observed. However, the decomposition had progressed faster in cases with microbial neoformation than in cases without signs of neoformation. Microbial neoformation may therefore act as an indicator of the decomposition rate within the early decomposition to bloating stages. This may be used in PMI estimation based on the total body score (TBS) and accumulated degree days (ADD) model, to potentially improve the model's precision.


Assuntos
1-Butanol/sangue , 1-Propanol/sangue , Acetaldeído/sangue , Restos Mortais , Etanol/sangue , Mudanças Depois da Morte , Adulto , Idoso , Idoso de 80 Anos ou mais , Cromatografia Gasosa/métodos , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Adulto Jovem
12.
Biotechnol Bioeng ; 117(9): 2771-2780, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32436991

RESUMO

4-Amino-1-butanol (4AB) serves as an important intermediate compound for drugs and a precursor of biodegradable polymers used for gene delivery. Here, we report for the first time the fermentative production of 4AB from glucose by metabolically engineered Corynebacterium glutamicum harboring a newly designed pathway comprising a putrescine (PUT) aminotransferase (encoded by ygjG) and an aldehyde dehydrogenase (encoded by yqhD) from Escherichia coli, which convert PUT to 4AB. Application of several metabolic engineering strategies such as fine-tuning the expression levels of ygjG and yqhD, eliminating competing pathways, and optimizing culture condition further improved 4AB production. Fed-batch culture of the final metabolically engineered C. glutamicum strain produced 24.7 g/L of 4AB. The strategies reported here should be useful for the microbial production of primary amino alcohols from renewable resources.


Assuntos
Amino Álcoois/metabolismo , Corynebacterium glutamicum/metabolismo , Engenharia Metabólica/métodos , Técnicas de Cultura Celular por Lotes/métodos , Corynebacterium glutamicum/genética , Redes e Vias Metabólicas , Putrescina/metabolismo
13.
Extremophiles ; 24(1): 121-133, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31654148

RESUMO

The fermentation of branched-chain amino acids (BCAAs) to branched-chain fatty acids (BCFAs) and branched-chain alcohols (BCOHs) is described using Thermoanaerobacter pseudoethanolicus. BCAAs were not degraded without an electron scavenging system but were degraded to a mixture of their BCFA (major) and BCOH (minor) when thiosulfate was added to the culture. Various environmental parameters were investigated using isoleucine as the substrate which ultimately demonstrated that at higher liquid-gas phase ratios the formation of 2-methyl-1-butanol from isoleucine achieved a maximal titer of 3.4 mM at a 1:1 liquid-gas ratio suggesting that higher partial pressure of hydrogen influences the BCOH/BCFA ratio but did not increase further with higher L-G phase ratios. Alternately, increasing the thiosulfate concentration decreased the BCOH to BCFA ratio. Kinetic monitoring of BCAA degradation revealed that the formation of BCOHs occurs slowly after the onset of BCFA formation. 13C2-labeled studies of leucine confirmed the production of a mixture of 3-methyl-1-butyrate and 3-methyl-1-butanol, while experiments involving 13C1-labeled 3-methyl-1-butyrate in fermentations containing leucine demonstrated that the carboxylic acid is reduced to the corresponding alcohol. Thus, the role of carboxylic acid reduction is likely of importance in the production of BCOH formation during the degradation of BCAA such as leucine.


Assuntos
Thermoanaerobacter , Álcoois , Aminoácidos de Cadeia Ramificada , Ácidos Graxos , Leucina
14.
Microb Cell Fact ; 19(1): 79, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-32220254

RESUMO

BACKGROUND: Owing to the increase in energy consumption, fossil fuel resources are gradually depleting which has led to the growing environmental concerns; therefore, scientists are being urged to produce sustainable and ecofriendly fuels. Thus, there is a growing interest in the generation of biofuels from renewable energy resources using microbial fermentation. MAIN TEXT: Butanol is a promising biofuel that can substitute for gasoline; unfortunately, natural microorganisms pose challenges for the economical production of 1-butanol at an industrial scale. The availability of genetic and molecular tools to engineer existing native pathways or create synthetic pathways have made non-native hosts a good choice for the production of 1-butanol from renewable resources. Non-native hosts have several distinct advantages, including using of cost-efficient feedstock, solvent tolerant and reduction of contamination risk. Therefore, engineering non-native hosts to produce biofuels is a promising approach towards achieving sustainability. This paper reviews the currently employed strategies and synthetic biology approaches used to produce 1-butanol in non-native hosts over the past few years. In addition, current challenges faced in using non-native hosts and the possible solutions that can help improve 1-butanol production are also discussed. CONCLUSION: Non-native organisms have the potential to realize commercial production of 1- butanol from renewable resources. Future research should focus on substrate utilization, cofactor imbalance, and promoter selection to boost 1-butanol production in non-native hosts. Moreover, the application of robust genetic engineering approaches is required for metabolic engineering of microorganisms to make them industrially feasible for 1-butanol production.


Assuntos
1-Butanol/metabolismo , Engenharia Genética/métodos
15.
Appl Microbiol Biotechnol ; 104(9): 3959-3969, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32185434

RESUMO

(R)-Selective ω-transaminase (ω-TA) is a key enzyme for the asymmetric reductive amination of carbonyl compounds to produce chiral amines which are essential parts of many therapeutic compounds. However, its practical industrial applications are hindered by the low catalytic efficiency and poor thermostability of naturally occurring enzymes. In this work, we report the molecular modification of (R)-selective ω-TA from Aspergillus terreus (AtTA) to allow asymmetric reductive amination of 4-hydroxy-2-butanone, producing (R)-3-amino-1-butanol. Based on substrate docking analysis, 4 residues in the substrate tunnel and binding pocket of AtTA were selected as mutation hotspots. The screening procedure was facilitated by the construction of a "small-intelligent" library and the use of thin-layer chromatography for preliminary screening. The resulting mutant AtTA-M5 exhibited a 9.6-fold higher kcat/Km value and 9.4 °C higher [Formula: see text] than that of wild-type AtTA. Furthermore, the conversion of 20 and 50 g L-1 4-hydroxy-2-butanone by AtTA-M5 reached 90.8% and 79.1%, suggesting significant potential for production of (R)-3-amino-1-butanol. Under the same conditions, wild-type AtTA achieved less than 5% conversion. Moreover, the key mutation (S215P in AtTA) was validated in 7 other (R)-selective ω-TAs, indicating its general applicability in improving the catalytic efficiency of homologous (R)-selective ω-TAs.


Assuntos
Amino Álcoois/metabolismo , Aspergillus/genética , Transaminases/genética , Transaminases/metabolismo , Aminação , Aspergillus/metabolismo , Catálise , Domínio Catalítico , Proteínas Fúngicas/genética , Proteínas Fúngicas/metabolismo , Cinética , Simulação de Acoplamento Molecular , Mutação , Ligação Proteica , Especificidade por Substrato
16.
Angew Chem Int Ed Engl ; 59(47): 21072-21079, 2020 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-32706141

RESUMO

The electroreduction of carbon dioxide using renewable electricity is an appealing strategy for the sustainable synthesis of chemicals and fuels. Extensive research has focused on the production of ethylene, ethanol and n-propanol, but more complex C4 molecules have been scarcely reported. Herein, we report the first direct electroreduction of CO2 to 1-butanol in alkaline electrolyte on Cu gas diffusion electrodes (Faradaic efficiency=0.056 %, j1-Butanol =-0.080 mA cm-2 at -0.48 V vs. RHE) and elucidate its formation mechanism. Electrolysis of possible molecular intermediates, coupled with density functional theory, led us to propose that CO2 first electroreduces to acetaldehyde-a key C2 intermediate to 1-butanol. Acetaldehyde then undergoes a base-catalyzed aldol condensation to give crotonaldehyde via electrochemical promotion by the catalyst surface. Crotonaldehyde is subsequently electroreduced to butanal, and then to 1-butanol. In a broad context, our results point to the relevance of coupling chemical and electrochemical processes for the synthesis of higher molecular weight products from CO2 .

17.
J Chem Ecol ; 45(7): 537-548, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31254146

RESUMO

Longhorn beetles are ecologically important insects in forest ecosystems as decomposers of woody substrates, microhabitat engineers, and as components of forest food webs. These species can be greatly affected both positively and negatively by modern forestry management practices, and should be monitored accordingly. Through headspace sampling, coupled gas chromatography-electroantennography, gas chromatography-mass spectrometry, and field bioassays, we identified two compounds, 2-methyl-1-butanol and 3-hydroxy-2-hexanone, that constitute aggregation-sex pheromone attractants of three cerambycid species which breed primarily in different types of fresh, recently dead oak wood in Northern Europe: Pyrrhidium sanguineum (L.), Phymatodes alni ssp. alni (L.), and Phymatodes testaceus (L.) (Cerambycinae: Callidiini). Analyses of headspace volatiles collected from live insects indicated that the male-produced aggregation-sex pheromone of P. sanguineum is a 1-15:100 blend of (R)-2-methyl-1-butanol and (R)-3-hydroxy-2-hexanone, whereas the corresponding ratios for P. alni were 70-110:100. In field bioassays, adult P. sanguineum and P. alni were significantly attracted to multiple blends with varying ratios of the two compounds. When tested individually, the compounds were minimally attractive. In contrast, adult P. testaceus exhibited nonspecific attraction to both of the individual compounds and to different blends, despite the hydroxyketone not being part of its pheromone, which consists of (R)-2-methyl-1-butanol alone. Overall, our results suggest that a blend of 50:100 of racemic 2-methyl-1-butanol and 3-hydroxy-2-hexanone is appropriate for parallel, cost-efficient pheromone-based monitoring of all three species. In particular, these species could serve as useful indicators of how modern forestry practices affect a whole guild of saproxylic insects that require ephemeral deadwood substrates for successful breeding.


Assuntos
Besouros/fisiologia , Atrativos Sexuais/química , Animais , Europa (Continente) , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Hexanonas/análise , Hexanonas/farmacologia , Masculino , Pentanóis/análise , Pentanóis/farmacologia , Atrativos Sexuais/farmacologia , Comportamento Sexual Animal/efeitos dos fármacos , Compostos Orgânicos Voláteis/química , Compostos Orgânicos Voláteis/farmacologia
18.
Regul Toxicol Pharmacol ; 107: 104406, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31238087

RESUMO

In this study, 48 herbal based products (41 for the pediatric population) were analyzed for the presence of ethanol and residual solvents. Ethanol was not detected in only 12% of the products designed for infants or toddlers aged under 2, and not quantified in only 5 of 14 'alcohol free' products. Actual content was higher than labeled in six out of 11 samples with specified ethanol quantity. WHO proposed requirement for ethanol content in products intended for use in children under the age of 6 (<0.5%) was not met by as many as 26 samples. Furthermore, calculated blood alcohol levels in children exceeded the relevant toxicological levels for nine samples following a single dose, and for one sample in case of accidental poisoning with the entire package. Regarding the residual solvents, acetone, 1-propanol and 1-butanol were not quantified, 2-propanol was found in two samples in low concentrations, whereas methanol intake via one of the samples exceeded the permitted level for children. The obtained results revealed a significant health concern for the pediatric population due to ethanol intake via herbal based products, calling for the establishment of strict guidelines for ethanol content and labeling.


Assuntos
Acetona/análise , Álcoois/análise , Preparações de Plantas/análise , Solventes/análise , Criança , Pré-Escolar , Qualidade de Produtos para o Consumidor , Humanos , Lactente , Medição de Risco
19.
Biochem Genet ; 57(3): 443-454, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30644007

RESUMO

3-Methyl-1-butanol (3MB) is a promising biofuel that can be produced from 2-ketoisocaproate via the common L-leucine biosynthesis pathway. Corynebacterium glutamicum was chosen as a host bacterium because of its strong resistance to isobutanol. In the current study, several strategies were designed to overproduce 3MB in C. glutamicum through a non-fermentation pathway. The engineered C. glutamicum mutant was obtained by silencing the pyruvate dehydrogenase gene complex (aceE) and deleting the lactic dehydrogenase gene (ldh), followed by mutagenesis with diethyl sulfate (DES) and selection with Fmoc-3-4-thiazolyl-L-alanine (FTA). The mutant could produce 659 mg/L of 3MB after 12 h of incubation. To facilitate carbon flux to 3MB biosynthesis, the engineered recombinant was also constructed without branched-chain acid aminotransferase (ilvE) activity by deleting the ilvE gene. This recombinant could produce 697 mg/L of 3MB after 12 h of incubation.


Assuntos
Corynebacterium glutamicum/genética , Corynebacterium glutamicum/metabolismo , Engenharia Genética , Mutação , Pentanóis/metabolismo , Cromossomos Bacterianos , Genes Bacterianos , Cetona Oxirredutases/genética
20.
Molecules ; 24(3)2019 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-30682770

RESUMO

Porous organic cages (POCs) have attracted extensive attention due to their unique structures and tremendous application potential in numerous areas. In this study, an enantioselective potentiometric sensor composed of a polyvinyl chloride (PVC) membrane electrode modified with CC3-R POC material was used for the recognition of enantiomers of 2-amino-1-butanol. After optimisation, the developed sensor exhibited enantioselectivity toward S-2-amino-1-butanol ( log K S , R P o t = -0.98) with acceptable sensitivity, and a near-Nernstian response of 25.8 ± 0.3 mV/decade within a pH range of 6.0⁻9.0.


Assuntos
Amino Álcoois/química , Técnicas Eletroquímicas , Eletrodos , Concentração de Íons de Hidrogênio , Membranas Artificiais , Estrutura Molecular , Cloreto de Polivinila/química , Porosidade , Potenciometria , Sensibilidade e Especificidade , Estereoisomerismo
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