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1.
Materials (Basel) ; 17(4)2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38399130

RESUMO

Plant-derived selenium is an important source of selenium (Se) for humans, which, however, has been restricted by a low content of Se in soil. Traditional Se fertilizers have tended to result in low selenium utilization. Thus, it was necessary to develop a new slow-release material to control Se fertilizer release. In this study, biochar pyrolyzed at 300 °C and 800 °C was cross-linked with polyethyleneimine (PEI) after being treated with HNO3 or NaOH (which were labeled Acid-W300, Acid-W800, Alkali-W300, and Alkali-W800). The results showed that the maximum adsorption capacities of Acid-W300, Alkali-W300, Acid-W800, and Alkali-W800 were 329.16 mg/g, 321.93 mg/g, 315.04 mg/g, and 344.33 mg/g, respectively. Among them, Acid-W800 and Alkali-W800 were mainly imine- and amide-bonded with SO32-, while Acid-W300 and Alkali-W300 were loaded with SO32- by forming the C-Se bonding as well as through imine- and amide-bonding. The release of four biochar-based selenium fertilizers in the red soil and brown soil extracts conformed to the pseudo-second-order kinetic model. The release rate and release amount of four biochar-based selenium fertilizers in the red soil extract were higher than those in the brown soil extract. Alkali-W800-Se had a higher proportion of Se-exchangeable release, accounting for 87.5% of the total loaded selenium, while Acid-W300-Se had the lowest proportion at 62.2%. However, the Se releases of Alkali-W800-Se were more than 42.49% and 37.67% of the total Se-loading capacity during 5 days of continuous red soil extraction and brown soil extraction, respectively. Acid-W300-Se released less than 20% of the total Se-loading capacity. Thus, Acid-W300-Se was the recommended slow-release Se fertilizer in red soil and brown soil.

2.
Food Chem X ; 19: 100807, 2023 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-37780243

RESUMO

This study evaluated the effects of hot air drying (HAD), microwave drying (MD), vacuum drying (VD), sun drying (SD) and vacuum freeze drying (VFD) on the physical properties, bioactive components, antioxidant capacity, volatile components and industrial application of coffee peel. The results showed VFD could retain the appearance color, total phenolics (19.49 mg GAE/g DW), total flavonoids (9.65 mg CE/g DW), caffeine (3.15 mg/g DW), trigonelline (2.71 mg/g DW), and antioxidant capacities of fresh sample to the greatest extent, but its operating cost was significantly higher than other treatments and total volatile components were in the minimum levels. HAD and SD exhibited the highest loss rates of total phenols and antioxidant capacities, exceeding 50%. MD offered the lowest operating cost, superior retention of bioactive components, and the richest variety and quantity of volatile compounds. Therefore, it is recommended to use MD to dehydrate the coffee peel in actual production.

3.
Org Lett ; 25(37): 6796-6801, 2023 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-37676817

RESUMO

A sustainable pathway for the synthesis of tetracyclic purinium salts via ruthenium-catalyzed electro-oxidative annulation of C6-arylpurine nucleosides with alkynes without a stoichiometric metal oxidant has been developed. The protocol described herein exhibits high regioselectivity, broad scope, and wide functional group tolerance, allowing efficient coupling of various biologically important molecules including acyclic, ribosyl, arabinosyl, and deoxyribosyl purine nucleoside derivatives. A novel purinoisoquinolinium-coordinated ruthenium(0) sandwich intermediate has been isolated, crystallographically characterized, and electrochemically analyzed, offering direct mechanistic insight.

4.
Sensors (Basel) ; 23(18)2023 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-37765795

RESUMO

The acoustic diffusion equation model has been widely applied in various scenarios, but a larger prediction error exists when applied to underground spaces, showing a significantly lower characteristic of the sound pressure level in the later stage compared to field tests since underground spaces have a more closed acoustic environment. Therefore, we analyze the characteristics of underground spaces differentiating from aboveground spaces when applying the model and propose an improved model from the perspective of energy balance. The energy neglected in the calculation of the acoustic diffusion equation model is compensated in long channel underground spaces named "acoustic escape compensation". A simulation and two field experiments are conducted to verify the effectiveness of the proposed compensation strategy in long-channel underground spaces. The mean square error is used to evaluate the differences between the classical model and the improved model, which shows a numerical improvement of 1.3 in the underground field test. The results show that the improved model is more suitable for describing underground spaces. The proposed strategy provides an effective extension of the acoustic diffusion equation model to solve the problem of sound field prediction and management in underground spaces.

5.
Bioresour Technol ; 386: 129483, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37454957

RESUMO

Improving the anaerobic treatment performance of waste activated sludge (WAS) to achieve resource recovery is an indispensable requirement to reduce carbon emissions, minimize and stabilize biosolids. In this study, a novel strategy by using urea hydrogen peroxide (UHP) to enhance SCFAs production through accelerating WAS disintegration, degrading recalcitrant substances and alleviating competitive suppression of methanogens. The SCFAs production and acetate proportion rose from 436.9 mg COD/L and 31.3% to 3102.6 mg COD/L and 54.1%, respectively, when UHP grew from 0 to 80 mg/g TSS. Mechanism investigation revealed that OH, O2 and urea were the major contributors to accelerate WAS disintegration with the sequence of OH> O2 > urea. Function microbes related to acidification and genes associated with acetate production ([EC:2.3.1.8] and [EC:2.7.2.1]) were upregulated while genes encoding propionic acid production ([EC:6.4.1.3] and [EC:6.2.1.1]) were downregulated. These results raised the application prospects of UHP in WAS resource utilization.


Assuntos
Ácidos Graxos Voláteis , Esgotos , Fermentação , Peróxido de Carbamida , Acetatos , Concentração de Íons de Hidrogênio
6.
Sci Total Environ ; 880: 163025, 2023 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-36966824

RESUMO

The presence of surfactants in waste activated sludge (WAS) system is generally regarded as beneficial to sludge treatment such as enhancing sludge dewatering and improving value-added fermentation products generation. However, in this study, it was firstly found that sodium dodecylbenzene sulfonate (SDBS, a typical surfactant) obviously increased toxic hydrogen sulfide (H2S) gas production from WAS anaerobic fermentation at environmentally relevant concentrations. Experimental results showed that H2S production from WAS significantly increased from 53.24 × 10-3 to 111.25 × 10-3 mg/g volatile suspended solids (VSS) when SDBS level increased from 0 to 30 mg/g total suspended solid (TSS). It was found that SDBS presence destroyed WAS structure and enhanced sulfur containing organics release. SDBS reduced the proportion of α-helix structure, damaged disulfide bridges and protein conformation, and effectively destroyed protein structure. SDBS promoted sulfur containing organics degradation and provided more readily hydrolyzed micro-molecule organics for sulfide production. Microbial analysis showed that SDBS addition enhanced the abundance of functional genes encoding protease, ATP-binding cassette transporters, and amino acids lyase, enhanced the activities and abundance of hydrolytic microbes, thus increased sulfide production from the hydrolysis of sulfur containing organics. Compared with the control, 30 mg/g TSS SDBS increased organic sulfurs hydrolysis and amino acids degradation by 47.1 % and 63.5 %, respectively. Key genes analysis further showed that SDBS addition promoted sulfate transport system and dissimilatory sulfate reduction. SDBS presence also lowered fermentation pH, promoted the chemical equilibrium transformation of sulfide, thus increased H2S gas release.


Assuntos
Sulfeto de Hidrogênio , Microbiota , Fermentação , Esgotos/química , Tensoativos/química , Ácidos Graxos Voláteis , Anaerobiose , Sulfetos , Lipoproteínas , Enxofre , Aminoácidos , Sulfatos , Concentração de Íons de Hidrogênio , Hidrogênio
7.
Int J Biol Macromol ; 224: 1412-1422, 2023 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-36550790

RESUMO

Superelastic silk fibroin (SF)-based aerogels can be used as multifunctional substrates, exhibiting a promising prospect in air filtration, thermal insulation, and biomedical materials. However, fabrication of the superelastic pure SF aerogels without adding synthetic polymers remains challenging. Here, the SF micro-nano fibrils (SMNFs) that preserved mesostructures are extracted from SF fibers as building blocks of aerogels by a controllable deep eutectic solvent liquid exfoliation technique. SMNFs can assemble into multiscale fibril networks during the freeze-inducing process, resulting in all-natural SMNF aerogels (SMNFAs) with hierarchical cellular architectures after lyophilization. Benefiting from these structural features, the SMNFAs demonstrate desirable properties including ultra-low density (as low as 4.71 mg/cm3) and superelasticity (over 85 % stress retention after 100 compression cycles at 60 % strain). Furthermore, the potential applications of superelastic SMNFAs in air purification and thermal insulation are investigated to exhibit their functionality, mechanical elasticity, and structural stability. This work provides a reliable approach for the fabrication of highly elastic SF aerogels and endows application prospects in air purification and thermal insulation opportunities.


Assuntos
Fibroínas , Seda , Fibroínas/química , Solventes Eutéticos Profundos , Géis/química , Materiais Biocompatíveis
8.
Environ Sci Technol ; 56(15): 10638-10645, 2022 08 02.
Artigo em Inglês | MEDLINE | ID: mdl-35839311

RESUMO

Persistent free radicals (PFRs) in biochar can influence biochar reactivity, promoting organic contaminant degradation or even causing certain toxic impacts. However, the PFR generation mechanism is not still well understood. An investigation of the relationship between PFR formation and the chemical structure of biochar is essential for understanding the PFR formation mechanism. Our in situ measurement results showed that PFR intensities increased from 0-509.5 to 146-5678 a.u. after being pyrolyzed at 300 °C for 60 min. The significant positive correlation between PFR intensities and the peak areas of C═O and aromatic C═C groups indicated that the generation of PFRs was highly dependent on the C═O and aromatic C═C structures. The reduction of biochars by KBH4 resulted in a 32.2 ± 2.49% decrease in the C═O content and a relative increase in the C-O content, while other physicochemical properties did not change. Thus, the observed 49.3% decrease in PFR signals after this reduction suggested that the reducible C═O groups, possibly in aldehydes, aromatic ketones, and quinones, were closely associated with PFRs in biochars. This study provides an in situ insight into the PFR generation mechanism and guides the corresponding biochar design and property manipulation.


Assuntos
Carvão Vegetal , Lignina , Carvão Vegetal/química , Radicais Livres/química
9.
Org Lett ; 24(23): 4234-4239, 2022 06 17.
Artigo em Inglês | MEDLINE | ID: mdl-35658480

RESUMO

Described herein is an efficient strategy for assembling a new library of functionalized polycyclic purinium salts with a wide range of anions through RhIII-catalyzed C-H activation/annulation of 6-arylpurine nucleosides with alkynes under mild reaction conditions. The resulting products displayed tunable photoluminescence covering most of the visible spectrum. Mechanistic insights delineated the rhodium catalyst's mode of action. A purinoisoquinolinium-coordinated rhodium(I) sandwich complex was well characterized and identified as the key intermediate.


Assuntos
Ródio , Alcinos , Catálise , Nucleosídeos , Sais
10.
Front Plant Sci ; 13: 848524, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35574077

RESUMO

Reasonable water and light management technology can improve economic benefits, coffee yield, and quality. We used cluster analysis and principal component analysis to evaluate and optimize the water and light management technology with high coffee yield, quality, and economic benefits in a subtropical monsoon climate region of China. The experiment was arranged in a randomized complete block design with two factors (3 irrigation levels × 4 shade cultivation treatments) replicated four times during 2016-2017. The irrigation levels consisted of full irrigation (FI) and two deficit irrigations (DI L : 75% FI, DI S : 50% FI). The shade cultivation treatments consisted of no shade cultivation (S0) and three shade cultivation modes (S L : intercropping with four lines of coffee and one line of banana; S M : intercropping with three lines of coffee and one line of banana; S S : intercropping with two lines of coffee and one line of banana). The results showed that the effects of irrigation level and shade cultivation mode on growth, crop yield, most of the photosynthetic characteristics, and nutritional quality were significant (p < 0.05). Regression analysis showed that the leaf radiation use efficiency (RUE) showed a significant negative exponential relation or logistic-curve variation with photosynthetically active radiation (PAR). The bean yield increased with an increase of the shade degree when water was seriously deficient, whereas it first increased and then decreased with an increase of the shade degree under FI and DI L . Based on both cluster analysis and principal component analysis, the FIS S treatment resulted in the highest comprehensive quality of coffee, followed by the FIS M treatment; the DI S S0 treatment obtained the lowest quality. Compared with the FIS0 treatment, the FIS M treatment increased the 2-year average bean yield and net income by 15.0 and 28.5%, respectively, whereas the FIS S treatment decreased these by 17.8 and 8.7%, respectively. To summarize, FIS S treatment significantly improved the nutritional quality of coffee, and FIS M treatment significantly increased the dry bean yield and economic benefits of coffee. The results of the study could provide a theoretical basis for water-saving irrigation and shade cultivation management of coffee in a subtropical monsoon climate region of China.

11.
J Org Chem ; 87(9): 6161-6178, 2022 05 06.
Artigo em Inglês | MEDLINE | ID: mdl-35438486

RESUMO

An electrochemical approach to promote the ortho-C-H alkylation of (hetero)arenes via rhodium catalysis under mild conditions is described. This approach features mild conditions with high levels of regio- and monoselectivity that tolerate a variety of aromatic and heteroaromatic groups and offers a widely applicable method for late-stage diversification of complex molecular architectures including tryptophan, estrone, diazepam, nucleosides, and nucleotides. Alkyl boronic acids and esters and alkyl trifluoroborates are demonstrated as suitable coupling partners. The isolation of key rhodium intermediates and mechanistic studies provided strong support for a rhodium(III/IV or V) regime.


Assuntos
Ródio , Alquilação , Catálise , Eletroquímica , Nucleosídeos , Nucleotídeos , Ródio/química
12.
Sci Total Environ ; 815: 152837, 2022 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-34995589

RESUMO

Urban wetland ecosystems are easily influenced by heavy metals (HMs) because of their functional properties. In this study, absolute principal component scores-multivariate linear regression (APCS-MLR) and positive matrix factorization (PMF) receptor models were applied for the source apportionment of available occurrence forms of heavy metals (AHMs) of surface sediments in a typical urban wetland of Dianchi Lake, southwest of China. The risk assessment was conducted to evaluate the potential ecological/human health risks of HMs. Results indicated that Zn, Pb, and Cr were the major pollutants affected by anthropogenic activities in sediments and their concentrations were significantly exceeding the background value. Most of the highly AHMs-polluted area was close to the river in wetland, and the concentration distribution of all AHMs were generally low in the southwest and high in the northeast. Both APCS-MLR and PMF models identified three comparable classes of potential sources, namely (1) agricultural fertilizer/insecticide, atmospheric deposition, and traffic emissions; (2) natural transitions; and (3) industrial and sewage wastes. Moreover, the comparison results implied that the PMF model was more feasible for quantifying AHMs sources in wetland sediments since it is capable to analyze one more source, namely plant maintenance and waterfowl feeding, and has higher accuracy in predicting the concentrations of AHMs. In addition, the risk assessment model revealed that all these HMs were within the acceptable ranges of ecological and carcinogenic/non-carcinogenic human health risks. Among these, ingestion was the major exposure pathway of HMs from local areas, followed by dermal exposure and oral or nasal inhalation. However, children were more easily exposed to HMs than adults by ingestion due to their hand-to-mouth behaviors. This study aims to assess the HM pollution status in a plateau urban wetland, and provides a practical case for modeling source apportionment and risk assessment of HMs in wetland sediments.


Assuntos
Metais Pesados , Áreas Alagadas , Criança , China , Ecossistema , Monitoramento Ambiental , Sedimentos Geológicos , Humanos , Metais Pesados/análise , Medição de Risco
13.
Phytomedicine ; 90: 153656, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-34332844

RESUMO

BACKGROUND: Herb-induced liver injury is a leading cause of drug-induced liver injury in China and its incidence is also increasing worldwide. Gardeniae Fructus (ZZ) has aroused wide concern for hepatotoxicity in recent decades. But when ZZ is administered in combination with Semen Sojae Praeparatum (DDC) to compose a herbal pair Zhizichi Decoction (ZZCD), lower hepatotoxicity is observed. The mechanism involved in the attenuated effect remains to be investigated. HYPOTHESIS/PURPOSE: Our previous studies showed that DDC benefited host metabolism by regulating the gut microbiota and it reduced the exposure of major toxic components of ZZ. The present study was aimed to investigate how DDC attenuated hepatotoxicity of ZZ from the perspective of gut microbiota. METHODS: Rats received ZZ and ZZCD treatment of different dosages and antibiotic treatment was applied to explore the involvement of gut microbiota. Biochemical assays and histopathological analysis were conducted to evaluate liver injury. Gut microbiota in caecal contents was profiled by 16S rRNA sequencing. Short-chain fatty acids (SCFAs) in caecal contents were measured by gas chromatography mass spectrometry (GCMS). To verify the protective effect of butyrate, it was administered with genipin, the major hepatotoxic metabolite of ZZ, to rats and HepG2 cells. Plasma lipopolysaccharide (LPS) level and colon tissue section were used to evaluate gut permeability. Expression level of Nuclear factor erythroid-derived 2-like 2 (Nrf2) was detected by immunohistochemistry in vitro and by western blot in vivo. RESULTS: Our study showed that ZZCD displayed lower hepatotoxicity than ZZ at the same dosage. ZZ induced gut dysbiosis, significantly reducing Lactobacillus and Enterococcus levels and increasing the Parasutterella level. In combination with DDC, these alterations were reversed and beneficial genus including Akkermansia and Prevotella were significantly increased. Besides, butyrate production was diminished by ZZ but was restored when in combination with DDC. Butyrate showed detoxification on genipin-induced liver injury by promoting colon integrity and promoting Nrf2 activation. Besides, it protected genipin-induced hepatocyte damage by promoting Nrf2 activation. CONCLUSION: DDC attenuates ZZ-induced liver injury by regulating the microbiota, promoting butyrate production and activating antioxidant response.


Assuntos
Antioxidantes/metabolismo , Butiratos/metabolismo , Doença Hepática Induzida por Substâncias e Drogas , Gardenia , Microbioma Gastrointestinal , /química , Animais , Doença Hepática Induzida por Substâncias e Drogas/tratamento farmacológico , Doença Hepática Induzida por Substâncias e Drogas/prevenção & controle , Frutas/toxicidade , Gardenia/toxicidade , RNA Ribossômico 16S , Ratos
14.
Org Lett ; 23(4): 1209-1215, 2021 02 19.
Artigo em Inglês | MEDLINE | ID: mdl-33538167

RESUMO

Electrochemically driven, Cp*Ir(III)-catalyzed regioselective annulative couplings of benzoic acids with alkynes have been established herein. The combination of iridium catalyst and electricity not only circumvents the need for stoichiometric amount of chemical oxidant, but also ensures broad reaction compatibility with a wide array of sterically and electronically diverse substrates. This electrochemical approach represents a sustainable strategy as an ideal alternative and supplement to the oxidative annulations methodology to be engaged in the synthesis of isocoumarin derivatives.

15.
Nat Commun ; 12(1): 930, 2021 02 10.
Artigo em Inglês | MEDLINE | ID: mdl-33568643

RESUMO

α-Pyridones and α-pyrones are ubiquitous structural motifs found in natural products and biologically active small molecules. Here, we report an Rh-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes, affording cyclic products in good to excellent yield. Divergent syntheses of α-pyridones and cyclic imidates are accomplished by employing N-phenyl acrylamides and N-tosyl acrylamides as substrates, respectively. Additionally, excellent regioselectivities are achieved when using unsymmetrical alkynes. This electrochemical process is environmentally benign compared to traditional transition metal-catalyzed C-H annulations because it avoids the use of stoichiometric metal oxidants. DFT calculations elucidated the reaction mechanism and origins of substituent-controlled chemoselectivity. The sequential C-H activation and alkyne insertion under rhodium catalysis leads to the seven-membered ring vinyl-rhodium intermediate. This intermediate undergoes either the classic neutral concerted reductive elimination to produce α-pyridones, or the ionic stepwise pathway to produce cyclic imidates.

16.
Ying Yong Sheng Tai Xue Bao ; 31(2): 515-523, 2020 Feb.
Artigo em Chinês | MEDLINE | ID: mdl-32476345

RESUMO

The fertilizer and shading management of Coffea arabica in dry-hot area is extensive, resulting in lower yield and fertilizer utilization efficiency. A field experiment was carried out to find the coupling mode of shading and fertilizer for fertilizer-saving and high yield of C. arabica in dry-hot region. Four shading levels (100% NR, 75% NR, 60% NR, 45% NR, NR was natural radiation) and four fertilizer levels (No fertilization and 666.67, 1000, 1333.33 kg·hm-2) were set to examine the effects of different radiations and fertilizer treatments on canopy structure, yield, ferti-lizer use efficiency, soil nutrient content and microbial biomass carbon of C. arabica. The results showed that canopy structure, yield, fertilizer use efficiency, soil nutrient content and microbial biomass carbon were significantly affected by shading and fertilizer treatments. Soil nutrient content and microbial biomass carbon decreased with the increases of shading levels. Soil nutrient content increased with the increases of fertilizer application, while microbial biomass carbon increased first and then decreased, with a peak at the rate of 1000 kg·hm-2(200.30 mg·kg-1). Shading and fertilizer had significant effects on the canopy structure including leaf area index and openness. There were significant negative correlations of leaf area index with openness, gap fraction, total fixed-point factor and total radiation under canopy. Results of response surface analysis and spatial analysis showed that the combination of shading level and fertilizer application were 80% NR and 666.67 kg·hm-2, 79% NR and 1286.81 kg·hm-2, 79% NR and 967.74 kg·hm-2, 82% NR and 1075.27 kg·hm-2, respectively, when partial fertilizer productivity, yield, fertilizer agronomic efficiency and yield increase of fertilizer reached the maximum. The ranges of shading and fertilizer were 68%-77% NR and 946.24-1178.79 kg·hm-2 when the yield, agronomic efficiency and yield increasing rate by fertilizer reached 80% of the maximum value. In this experiment, the optimum combination of shading level and fertilizer application was 75% NR and 1000 kg·hm-2.


Assuntos
Coffea , Fertilizantes , Agricultura , Biomassa , China , Nitrogênio , Solo
17.
Acc Chem Res ; 53(2): 300-310, 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-31939278

RESUMO

Electrochemical synthesis of organic compounds has emerged as an attractive and environmentally benign alternative to conventional approaches for oxidation and reduction of organic compounds that utilizes electric current instead of chemical oxidants and reductants. As such, many useful transformations have been developed, including the Kolbe reaction, the Simons fluorination process, the Monsanto adiponitrile process, and the Shono oxidation, to name a few. Electrochemical C-H functionalization represents one of the most promising reaction types among many electrochemical transformations, since this process avoids prefunctionalization of substrates and provides novel retrosynthetic disconnections. However, site-selective anodic oxidation of C-H bonds is still a fundamental challenge due to the high oxidation potentials of C-H bonds compared to organic solvents and common functional groups. To overcome this issue, indirect electrolysis via the action of a mediator (a redox catalyst) is regularly employed, by which the selectivity can be controlled following reaction of said mediator with the substrate. Since the redox potentials of transition metal complexes can be easily tuned by modification of the ligand, the synergistic use of electrochemistry and transition metal catalysis to achieve site-selective C-H functionalization is an attractive strategy. In this Account, we summarize and contextualize our recent efforts toward transition metal-catalyzed electrochemical C-H functionalization proximal to a suitable directing group. We have developed C-H oxygenation, acylation, alkylation, and halogenation reactions in which a Pd(II) species is oxidized to a Pd(III) or Pd(IV) intermediate by anodic oxidation, followed by reductive elimination to form the corresponding C-O, C-C, and C-X bonds. Importantly, improved monofunctionalization selectivity is achieved in the Pd-catalyzed C(sp3)-H oxygenation compared to conventional approaches using PhI(OAc)2 as the chemical oxidant. Physical separators are sometimes used to prevent the electrochemical deposition of Pd black on the cathode resulting from reduction of high valent Pd species. We skirted this issue through the development a Cu-catalyzed electrochemical C(sp2)-H amination using n-Bu4NI as a redox cocatalyst in an undivided cell. In addition, we developed Ir-catalyzed electrochemical vinylic C-H functionalization of acrylic acids with alkynes in an undivided cell, affording various substituted α-pyrones in good to excellent yield. More importantly, chemical oxidants, including Ag2CO3, Cu(OAc)2, and PhI(OAc)2, resulted in much lower yields in the absence of electrical current under otherwise identical conditions. As elaborated below, progress in the area of electrochemical transition metal-catalyzed synthesis provides an effective platform for environmentally friendly and sustainable selective chemical transformations.

18.
J Org Chem ; 85(5): 3497-3507, 2020 03 06.
Artigo em Inglês | MEDLINE | ID: mdl-31889446

RESUMO

A simple and mild protocol for copper-catalyzed bromination of quinoline at the C5 site of quinoline by anodic oxidation was developed, affording the desired remote C-H activation products with isolated yields of up to about 90%. The reaction proceeds with low-cost NH4Br and shows mild and green conditions (electricity as a green oxidant; NH3 and H2 as byproducts). At the same time, a gram-scale bromination reaction was also successfully fulfilled, showing its potential applicable value in organic synthesis. Moreover, the CV chart further demonstrated the proposed catalytic cycle.

19.
Environ Res ; 181: 108899, 2020 02.
Artigo em Inglês | MEDLINE | ID: mdl-31740041

RESUMO

In this work, corn straw (CS) based porous carbon was prepared by one-step phosphoric acid (H3PO4) low temperature activation. The impregnation ratios (H3PO4/CS, g/g) played an important role in the pore development. ACS300-1 engineered at 300 °C and the impregnation ratio of 1.0 showed the maximal specific surface area of 463.89 m2/g with total pore volume of 0.387 cm3/g, attaining a high tetracycline (TC) uptake of 227.3 mg/g. The adsorption of TC onto ACS300-1 was found tolerant with wide pH (2.0-10.0) and high ionic strength (0 - 0.5 M). The adsorption data can be fitted well by the pseudo-second order kinetic model and Langmuir isotherm model. The endothermic and spontaneous properties of the adsorption system was implied by Thermodynamic study. The findings of the current work conclude that one-step H3PO4 activation is a green and promising method for corn straw based porous carbon that may be found with great potentials in antibiotic containing wastewater treatment.


Assuntos
Antibacterianos , Carbono , Tetraciclina , Poluentes Químicos da Água , Adsorção , Concentração de Íons de Hidrogênio , Cinética , Ácidos Fosfóricos , Porosidade , Temperatura , Zea mays
20.
Biotechnol Biofuels ; 12: 256, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31687044

RESUMO

BACKGROUND: Trametes trogii is a member of the white-rot fungi family, which has a unique ability to break down recalcitrant lignin polymers to CO2 and water, and they have enormous potential to biodegrade a wide range of toxic environmental pollutants. Because of its industrial potential, the identification of lignin-degrading enzyme systems in Trametes is an important area of research. Development and utilization of industrial value genes are suffering due to deficiency knowledge of genome available for their manipulation. RESULTS: In the present study, Homokaryotic strains of T. trogii S0301 were screened and sequencing by PacBio Sequel II platform. The final draft genome is ~ 39.88 Mb, with a contig N50 size of 2.4 Mb, this was the first genome sequencing and assembly of T. trogii species. Further analyses predicted 14,508 protein-coding genes. Results showed that T. trogii S0301 contains 602 genes encoding CAZymes, include 211 glycoside hydrolase and 117 lignin-degrading family genes, nine laccases related genes. Small subunit ribosomal RNA gene (18S rRNA) sequencing confirms its phylogenetic position. Moreover, T. trogii S0301 has the largest number of cytochromes P450 (CYPs) superfamily genes compare to other fungi. All these results are consistent with enzymatic assays and transcriptome analysis results. We also analyzed other genome characteristics in the T. trogii S0301genome. CONCLUSION: Here, we present a nearly complete genome for T. trogii S0301, which will help elucidate the biosynthetic pathways of the lignin-degrading enzyme, advancing the discovery, characterization, and modification of novel enzymes from this genus. This genome sequence will provide a valuable reference for the investigation of lignin degradation in the Trametes genus.

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