NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 24
·10959-10970
·
IF 3.591
Sethupathi Shanmugasundaram,Hairus Abdullah,Noto Susanto Gultom,Hardy Shuwanto,Dong-Hau Kuo
Hydrogen is an inevitable energy source to replace fossil fuels in the future. Herein, we report Ni-doped ZnIn2(O,S)4/In(OH)3 heterojunction composites with different sulfur contents to support green hydrogen gas evolution. A simple one-step hydrothermal preparation process was carried out by simultaneously adding all chemical precursors during the synthesis of composites. The as-prepared composites were carefully characterized by XRD, FE-SEM, TEM, XPS, DRS, TPC, MS, EIS and CV techniques, which confirmed their performance in the hydrogen evolution reaction (HER) under visible-light illumination. With increasing sulfur content, XRD analysis indicated the gradual formation of Ni-doped ZnIn2(O,S)4 co-existing with the In(OH)3 phase. The highest hydrogen evolution rate of 2100 μmol g−1 h−1 under visible-light illumination was achieved in the presence of the Ni-doped ZnIn2(O,S)4/In(OH)3 composite. Its excellent photocatalytic performance is related to the good separation of photocarriers. XPS analysis suggests the formation of positively and negatively charged defects on catalyst surfaces which attract the photogenerated electrons and holes, respectively, thus leading to an extended photocarrier lifetime. Furthermore, the coupling effect with In(OH)3 provides a more positive conduction band (CB) relative to that of the Ni-doped ZnIn2(O,S)4 phase for facile electron transfer. A plausible HER mechanism based on the experimental data is proposed in this work.
研究领域:
材料科学
·
能源化学
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产品关联
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2021
·
IF 9.642
Qiang Chen,Mingzhao Guo,Yuexin Bi,Ge Qu,Zhoutong Sun,Yujun Wang,Guangsheng Luo
This work aims to synthesize S -(4-chlorophenyl)-(pyridin-2-yl) methanol ( S -CPMA) in a green, economic, and efficient way. In the water–cyclohexane liquid–liquid system, recombinant Escherichia coli ( E. coli ) was used as a whole-cell catalyst and retained > 60% of its catalytic activity after five reuse cycles. In situ accumulation of the substrate/product in the organic phase effectively improves substrate tolerance and reduces product inhibition and toxicity. Meanwhile, a microreaction system consisting of membrane dispersion and three-dimensional (3D) bending-microchannel was developed to successfully generate droplet swarms with an average diameter of 30 μm. Large specific surface area provided high mass transfer efficiency between phases. While the analogous reaction in a traditional stirred tank required > 270 min to achieve a yield of > 99%, in this biphasic microreaction system, the yield reached 99.6% with a high enantiomeric excess (ee) of > 99% in only 80 min. Efficient synthesis was achieved by reducing the time by 70%.
研究领域:
生物化学
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合成生物学
·
绿色化学
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产品关联
DOI
PubMed
高影响因子
ORGANIC PROCESS RESEARCH & DEVELOPMENT
·
2020
·
IF 3.023
Zeyu Yang,Wenjie Ye,Youyu Xie,Qinghai Liu,Rong Chen,Hualei Wang,Dongzhi Wei
Bioreductions catalyzed by alcohol dehydrogenases (ADHs) play an important role in the synthesis of chiral alcohols. However, the synthesis of ethyl (S)-4-chloro-3-hydroxybutyrate [(S)-CHBE], an important drug intermediate, has significant challenges concerning high substrate or product inhibition toward ADHs, which complicates its production. Herein, we evaluated a novel ADH, SmADH31, obtained from the Stenotrophomonas maltophilia genome, which can tolerate extremely high concentrations (6 M) of both substrate and product. The coexpression of SmADH31 and glucose dehydrogenase from Bacillus subtilis in Escherichia coli meant that as much as 660 g L–1 (4.0 M) ethyl 4-chloroacetoacetate was completely converted into (S)-CHBE in a monophasic aqueous system with a >99.9% ee value and a high space-time yield (2664 g L–1 d–1). Molecular dynamics simulation shed light on the high activity and stereoselectivity of SmADH31. Moreover, five other optically pure chiral alcohols were synthesized at high concentrations (100–462 g L–1) as a result of the broad substrate spectrum of SmADH31. All these compounds act as important drug intermediates, demonstrating the industrial potential of SmADH31-mediated bioreductions.
研究领域:
生物化学
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药物化学
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酶工程
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DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Xuecai Wei,Xiaoyang Yue,Quan Yuan,Ying He,Li Ma,Liya Zhou,Guanhua Liu,Yunting Liu,Yanjun Jiang
Ethyl ( S )-4‑chloro-3-hydroxybutyrate [( S )-CHBE] is attractive as a necessary intermediate for the production of highly valued products in pharmaceutical industries. Nowadays, alcohol dehydrogenases play an increasingly essential role in the asymmetric synthesis of chiral alcohols. In this work, a nicotinamide adenine dinucleotide (NADH)-dependent alcohol dehydrogenase from Pseudomonas bacterium ( Pb ADH) was obtained by genome mining method and identified to exhibit an excellent tolerance against the high substrate and product concentrations. For the regeneration of NADH, Bacillus megaterium glucose dehydrogenase ( Bm GDH) was successfully co-expressed with Pb ADH in E. coli cells. So much as 3.5 M (574 g/L) ethyl 4-chloroacetoacetate (COBE) can be converted to ( S )-CHBE completely with a > 99 % ee value under the catalysis by recombinant cells, even in a monophasic aqueous media with a single batch charge of substrate. In addition, in order to verify the substrate scope of Pb ADH, six other α/β-ketone esters and aromatic ketones were also evaluated as substrates at high substrate concentrations (100–650 g/L), and the corresponding chiral alcohols with highly optical purity were also achieved by co-expressed E. coli cells.
研究领域:
生物化学
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酶工程
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制药工业
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产品关联
DOI
高影响因子
BIOCHEMICAL ENGINEERING JOURNAL
·
2015
·
IF 2.467
Qin Xu,Wei-Yi Tao,He Huang,Shuang Li
An NADPH-dependent carbonyl reductase (YlCR2) from Yarrowia lipolytica was discovered by genome mining, overexpressed in Escherichia coli BL21 and purified to homogeneity. To efficiently synthesize ethyl ( S )-4-chloro-3-hydroxybutanoate (( S )-CHBE) (99%, e.e), the highly stereoselective bioreduction of ethyl 4-chloro-3-oxobutanoate (COBE) into ( S )-CHBE with the recombinant E. coli BL21/pETYlCR2 was successfully demonstrated in an n -butyl acetate-water biphasic system (1:1, v/v) with NADPH self-regeneration by substrate-coupled system using sorbitol or mannitol as co-substrate. The optimum reaction condition for the biotransformation of COBE in the biphasic system were 3000 mM COBE, (1.2 or 1.3 mmol/mmol COBE) mannitol or sorbitol, 0.2 mM or 0.4 mM NADP + , 0.12 or 0.14 g (wet weight)/ml cell dosage, pH 5.0, 30 °C; ( S )-CHBE with yield of 90% and e.e of 99% was obtained after 10 h reaction. Furthermore, 3000 mM COBE could also be completely biotransformed after 20 h without addition of expensive cofactor NADP + . Significantly, E. coli BL21/pETYlCR2 shows the high potential in the industrial production of ( S )-CHBE.
研究领域:
生物化学
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合成生物学
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酶工程
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DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2015
·
IF 4.494
Yu-Cai He,Dan-Ping Zhang,Zhi-Cheng Tao,Yun Lu,Yun Ding,Feng Liu,Zheng-Zhong Zhu,Huan Rui,Gao-Wei Zheng,Xian Zhang
To reduce dependence on the expensive cofactor and effectively biotransform ethyl 4-chloro-3-oxobutanoate, l -glutamine and glycine were found to enhance the content of intracellular NADH and the reductase activity. Adding the mixture of 200 mM of l -glutamine and 500 mM of glycine to the reaction media, a 1.67-fold of reductase activity was increased over the control without the addition of the two compounds. Moreover, β-cyclodextrin (0.4 mol β-cyclodextrin/mol ethyl 4-chloro-3-oxobutanoate) was also added into this reaction media, and the biocatalytic activity of the whole-cell biocatalyst of Escherichia coli CCZU-K14 was increased by 1.34-fold than that without β-cyclodextrin. In this β-cyclodextrin–water media containing l -glutamine (200 mM) plus glycine (500 mM), ethyl ( S )-4-chloro-3-hydroxybutanoate (>99% ee ) could be obtained from 3000 mM ethyl 4-chloro-3-oxobutanoate in the yield of 98.0% after 8 h. All the positive features demonstrate the potential applicability of the bioprocess for the large-scale production of ethyl ( S )-4-chloro-3-hydroxybutanoate.
研究领域:
生物化学
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酶工程
·
有机合成
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产品关联
DOI
PubMed
高影响因子
Bioresource Technology Reports
·
2018
·
IF 0
Bing-Qian Wang,Bo Peng,Jian-Fei Sun,Chu Wang,Ke Jiang,Jing-Hao Ma,Peng-Qi Zhang,Yu-Cai He
An effecti v e combination pretreatment of bamboo shoot shell (BSS) using Emulsifier OP-10 (0.5%, w/v) in the acidified media (pH 4.0) by autoclaving (120 °C, 40 min) was conducted. After BSS slurry without detoxification was enzymatically hydrolyzed for 96 h, glucose (25.2 g/L) and xylose (7.5 g/L) were obtained from 50 g/L BSS at high yields. HPLC results showed that no potential inhibitors (furfural and 5-hydroxymethylfurfural) formed. In the hydrolysates , an effective biocatalytic synthesis of ethyl ( S )-4-chloro-3-hydroxybutanoate (100% yield; >99% e.e. ) from 1000 mM ethyl 4-chloro-3-oxobutanoate was developed without the extra addition of cofactors within 24 h. In summary, this combination strategy involving biomass pretreatment, enzymatic saccharification , and bioreduction can be developed for producing chiral alcohols.
研究领域:
生物质预处理
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酶解糖化
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生物催化
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手性醇合成
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DOI
BIORESOURCE TECHNOLOGY
·
2014
·
IF 5.039
Yu-Cai He,Zhi-Cheng Tao,Xian Zhang,Zhen-Xing Yang,Jian-He Xu
An NADH-dependent reductase (CmCR) from Candida magnoliae was discovered by genome mining for carbonyl reductases. After CmCR was overexpressed in Escherichia coli BL21, a robust reductase-producing strain, recombinant E. coli CCZU-K14, was employed for the efficient synthesis of ethyl ( S )-4-chloro-3-hydroxybutanoate (( S )-CHBE) from the reduction of ethyl 4-chloro-3-oxobutanoate (COBE). After the optimization, the optimum reaction conditions were obtained. Notably, E. coli CCZU-K14 had broad substrate specificity in reducing both aliphatic and aromatic substrates, and excellent enantioselectivity of CCZU-K14 was observed for most of the tested substrates, resulting in chiral alcohols of over 99.9% ee . Moreover, COBE at a high concentration of (3000 mM) could be asymmetrically reduced to ( S )-CHBE in the high yield (>99.0%) and high enantiometric excess value (>99.9% ee ) after 14 h. Significantly, E. coli CCZU-K14 shows high potential in the industrial production of ( S )-CHBE and its derivatives (>99.9% ee ).
研究领域:
生物化学
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合成生物学
·
酶工程
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DOI
PubMed
高影响因子
APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY
·
2014
·Vol. 173
·期 8
·2042-2053
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IF 1.687
He Yu-Cai,Yang Zhen-Xing,Zhang Dan-Ping,Tao Zhi-Cheng,Chen Chao,Chen Yi-Tong,Guo Fei,Xu Jian-He,Huang Lei,Chen Rui-Jie,Ma Xiao-Feng
The reductase (PgCR) from recombinant Escherichia coli CCZU-Y10 displayed high reductase activity and excellent stereoselectivity for the reduction of ethyl 4-chloro-3-oxobutanoate (COBE) into ethyl ( S )-4-chloro-3-hydroxybutanoate (( S )-CHBE). To efficiently synthesize ( S )-CHBE (>99 % enantiomeric excess (ee)), the highly stereoselective bioreduction of COBE into ( S )-CHBE with the whole cells of E. coli CCZU-Y10 was successfully demonstrated in a dibutyl phthalate-water biphasic system. The appropriate ratio of the organic phase to water phase was 1:1 ( v / v ). The optimum reaction temperature, reaction pH, cosubstrate, NAD + , and cell dosage of the biotransformation of 100 mM COBE in this biphasic system were 30 °C, 7.0, mannitol (2.5 mmol/mmol COBE), 0.1 μmol/(mmol COBE), and 0.1 g (wet weight)/mL, respectively. Moreover, COBE at a high concentration of (1,000 mM) could be asymmetrically reduced to ( S )-CHBE in a high yield (99.0 %) and high enantiometric excess value (>99 % ee). Significantly, E. coli CCZU-Y10 shows high potential in the industrial production of ( S )-CHBE (>99 % ee).
研究领域:
生物化学
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微生物学
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合成生物学
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DOI
PubMed
高影响因子
APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY
·
2016
·Vol. 181
·期 4
·1347-1359
·
IF 1.606
Dai Yong,Huan Bin,Zhang Hai-Sheng,He Yu-Cai
To increase the biocatalytic activity of Escherichia coli CCZU-T15 whole cells, choline chloride/glycerol ([ChCl][Gly]) was firstly used as biocompatible solvent for the effective biotransformation of ethyl 4-chloro-3-oxobutanoate (COBE) into ethyl ( S )-4-chloro-3-hydroxybutanoate [( S )-CHBE]. Furthermore, L-glutamine (150 mM) was added into [ChCl][Gly]–water ([ChCl][Gly] 12.5 vol%, pH 6.5) media instead of NAD + for increasing the biocatalytic efficiency. To further improve the biosynthesis of ( S )-CHBE (>99 % e.e. ) by E. coli CCZU-T15 whole cells, Tween-80 (7.5 mM) was also added into this reaction media, and ( S )-CHBE (>9 % e.e. ) could be effectively synthesized from 2000 and 3000 mM COBE in the yields of 100 and 93.0 % by whole cells of recombinant E. coli CCZU-T15, respectively. TEM image indicated that the cell membrane was permeabilized and lost its integrity and when the cell was exposed to [ChCl][Gly]–water media with Tween-80. Clearly, this bioprocess has high potential for the effective biosynthesis of ( S )-CHBE (>99 % e.e. ).
研究领域:
生物化学
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合成生物学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES
·
2024
·
IF 2.8
Fei Yang,Yi-Yi Cao,Jing Xi,Yang Luan,Na Li,Xin Dong,Xin-Yu Zhang
1,3-Butadiene (BD) is a carcinogenic air pollutant. N -acetyl- S -(4-hydroxy-2-buten-1-yl)-L-cysteine (MHBMA3 or 4HBeMA), an urinary BD metabolite with unspecified configuration, is considered the most sensitive BD biomarker and has been used in routine biomonitoring since 2012. However, two issues remain unaddressed: why its concentrations are unusually high relative to other urinary BD biomarkers and why some authors reported no detection of the biomarker whereas other authors readily quantitated it. To address the issues, we synthesized and structurally characterized the authentic trans - and cis -isomers of MHBMA3 (designated NE and NZ, respectively), developed an isotope-dilution LC-MS/MS method for their quantification, and examined 67 urine samples from barbecue restaurant personnel (n = 47) and hotel administrative staff (n = 20). The restaurant personnel were exposed to barbecue fumes, which contain relatively high concentrations of BD. The results showed that NE and NZ had highly similar NMR spectra, and were difficult to be well separated chromatographically. The NMR data showed that the MHBMA3 isomer investigated in most previous studies was NE. We did not detect NE and NZ in any samples; however, an interfering peak with varying heights was observed in most samples. Notably, under the chromatographic conditions used in the literature, the peak exhibited indistinguishable retention time from that of NE. Thus, it is highly likely that the interfering peak has been mis-identified as NE in previous studies, providing a reasonable explanation for the high MHBMA3 concentration in urine. The contradiction in the presence of MHBMA3 in urine was also caused by the mis-identification, because the researchers who reported the absence of MHBMA3 were actually detecting NZ. Thus, we clarified the confusion on MHBMA3 in previous studies through correctly identifying the two MHBMA3 isomers. The presence of NE and NZ in human urine warrants further investigations.
研究领域:
环境科学
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分析化学
·
毒理学
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产品关联
DOI
PubMed
高影响因子
BIORESOURCE TECHNOLOGY
·
2016
·
IF 4.917
Yu-Cai He,Dan-Ping Zhang,Jun-Hua Di,Yin-Qi Wu,Zhi-Cheng Tao,Feng Liu,Zhi-Jun Zhang,Gang-Gang Chong,Yun Ding,Cui-Luan Ma
In this study, sugarcane bagasse (SB) was pretreated with combination pretreatment (e.g., sequential KOH extraction and ionic liquid soaking, sequential KOH extraction and Fenton soaking, or sequential KOH extraction and glycerol soaking). After the enzymatic hydrolysis of pretreated SBs, it was found that all these three concentrated hydrolyzates could be used for the asymmetric bioreduction of ethyl 4-chloro-3-oxobutanoate (COBE) into ethyl ( S )-4-chloro-3-hydroxybutanoate [( S )-CHBE]. Compared with glucose, arabinose and cellobiose couldn’t promote the initial reaction rate, and xylose could increase the intracellular NADH content. Moreover, it was the first report that hydrolyzates could be used for the effective biosynthesis of ( S )-CHBE (∼500 g/L; 98.0% yield) from 3000 COBE by whole cells of Escherichia coli CCZU-K14 in the presence of β-CD (0.4 mol β-CD/mol COBE), l -glutamine (200 mM) and glycine (500 mM). In conclusion, it is a new alternative to utilize bioresource for the synthesis of key chiral intermediate ( S )-CHBE.
研究领域:
生物技术
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生化工程
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有机化学
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微生物学
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）