ORGANIC & BIOMOLECULAR CHEMISTRY
·
2022
·Vol. 20
·期 25
·5104-5114
·
IF 3.89
Jin-Rong Lai,Fu-Dan Yin,Qing-Song Guo,Fei Yuan,Bei-Fang Nian,Ming Zhang,Zhi-Bang Wu,Hong-Bin Zhang,E Tang
An Ag-catalysed three-component reaction of alkynyl aryl ketones bearing an ortho-methoxy group, element selenium, and arylboronic acid, providing a facile route to selenofunctionalized chromone products has been developed. This protocol features high efficiency and high regioselectivity, and the use of selenium powder as the selenium source. Mechanistic experiments indicated that the combined oxidative effect of (bis(trifluoroacetoxy)iodo)benzene and oxygen in the air pushes the catalytic redox cycle of the Ag catalyst and the phenylselenium trifluoroacetate formed in situ is the key intermediate of the PIFA-mediated 6-endo-electrophilic cyclization and selenofunctionalization reaction of alkynyl aryl ketones.
研究领域:
有机化学
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药物化学
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DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Guosi Li,Wei Wang,Heng Guo,Shanyong Yi,Fang Wang,Shiping Huang,Nan Hu,Qilin Xu,Yongjun Zang,Bangxing Han,Xinjian Yin
Microbial glycosyltransferases efficiently synthesize glucosides and have garnered increasing interest. However, limited regioselectivity has impeded their broad application, particularly in the pharmaceutical industry. In this study, the UDP-glycosyltransferase YjiC from Bacillus licheniformis ( Bl YjiC) was engineered to achieve the bidirectional regioselective glycosylation of tyrosol and its derivatives. Initially, site-directed saturation mutagenesis was performed on two newly identified substrate-binding cavities in the acceptor pocket of Bl YjiC to provide a comprehensive blueprint of the interplay between mutations and function (mutability landscape). Iterative saturation mutagenesis was performed, guided by the mutability landscape. Two highly regioselective mutants M6 (M112L/I325Y/L70R/Q136E/I67E/M77R) and M2’ (M112D/I62L) were generated, exhibiting >99 % regioselectivity toward the alcoholic and phenolic hydroxyl of tyrosol, respectively, compared with the wild-type (product mixture: 51:49 %). Both mutants exhibited excellent regioselectivity toward several dihydroxy phenolic substrates, offering valuable biocatalysts for the regioselective synthesis of glucosides. Their application was confirmed in a short synthesis of salidroside (3.6 g/L) and icariside D2 (2.4 g/L), which exhibited near-perfect regioselectivity. This study provides valuable insights into future protein engineering of similar enzymes and opens new avenues for their practical applications.
研究领域:
生物化学
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合成生物学
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制药工程
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR CATALYSIS B-ENZYMATIC
·
2013
·
IF 2.823
Chen Hui Du,Jian Zhang,Shao Hua Xu,Xu Dong Wang,Jun Ping Kou,Bo Yang Yu
This study explored the substrate scope and regio-selectivity of Gliocladium deliquescens NRRL 1086 on hydroxylated benzophenones (HBPs), which was the follow-up investigation on the glycosylation of phenolic hydroxyl compounds by this unique microbe. Five HBPs substrates were used and three glycosylated metabolites, iriflophenone 2- O - β - d -glycopyranoside ( 6 , 40%), riflophenone 4- O - β - d -glycopyranoside( 7 , 21%) and 2,6,4′-trihydroxy-4-methoxybenzophenone-2- O - β - d -glycopyranoside ( 8 , 65%) were isolated and structurally identified unambiguously by ESI-MS, 1 H NMR, 13 C NMR, and 2D NMR spectroscopy. The versatile glycosylation ability of G. deliquescens NRRL 1086 on phenolic hydroxyl compounds may provide an alternative and convenient method to enable high-efficiency synthesis of various HBPs glycosides.
研究领域:
微生物学
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天然产物化学
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生物合成
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产品关联
DOI
高影响因子
CHROMATOGRAPHIA
·
2012
·Vol. 75
·期 23
·1347-1354
·
IF 1.195
Sun Baishen,Li Xiaofang,Jin Zhaolei,Tian Lili,Wang Fang,Liu Guihua,Tang Shouwan,Pan Fuyou
Four regioselectively modified amylose derivatives with three different substituents at the 2-, 3-, and 6-positions were prepared and their enantioseparations in HPLC were examined. Investigations indicated that the nature as well as the arrangement of the substituents significantly influenced their enantioseparations and each derivative exhibited characteristic chiral recognition. Amylose 2-benzoyl-3-(3,5-dimethylphenylcarbamate or 3,5-dichlorophenylcarbamate)-6-(( S )-1-phenylethylcarbamate) exhibited chiral resolving abilities comparable to the commercial available amylose tris(3,5-dimethylphenylcarbamate)-based column, Chiralpak AD and the racemic compounds shown in this study were most effectively resolved on these two derivatives. The influence of mobile phase on chiral resolution was also examined.
研究领域:
化学
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分析化学
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色谱技术
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产品关联
DOI
高影响因子
PROCESS BIOCHEMISTRY
·
2024
·
IF 3.7
Chuang Li,Xian Zhang,Yuqing Wang,Qingtao Liu,Zhou Wang,Rui Huang,Zhenglian Xue
To enrich ‘epoxide hydrolase (EH) tool cabinet’ for preparing enantiopure epoxides and 1,2-diols, a novel microbial EH, Sf EH2, was identified from Streptomyces fradiae SF-2. Bioinformatics analysis indicated that Sf EH2 has typical structural characteristics of α/β-hydrolase fold superfamily. Its coding gene, sfeh 2, was then codon-optimized and amplified. A recombinant (re) Sf EH2-expressing E. coli BL21(DE3) strain ( E. coli / sfeh 2) was constructed through DNA manipulations. Substrate spectrum assay including fifteen common racemic ( rac -) epoxides by E. coli / sfeh 2 showed that re Sf EH2 displayed the highest and best complementary regioselectivities (regioselectivity coefficients, α R = 89.7% and β S = 91.4%) towards rac - 14a , as well as the highest enantioselectivity (enantiomeric ratio, E = 15.3) in S -type towards rac - 15a . Molecular docking simulation revealed that Sf EH2 preferentially attacked C α of ( R )- 14a and C β of ( S )- 14a geometrically. In kinetic parameter analysis, the K m R (5.74 mM) of purified re Sf EH2 for ( R )- 15a was 1.76-fold lower than K m S (10.09 mM) for ( S )- 15a . At last, using 50 mg dry cell weight/mL E. coli / sfeh 2, the scale-up enantioconvergent hydrolysis of 100 mM rac - 14a at 30 °C for 6.0 h afforded ( S )- 14b with 80.9% ee p and 90.1% yield, while the kinetic resolution of 150 mM rac - 15a retained ( S )- 15a with >99.0% ee s and 42.2% yield.
研究领域:
生物化学
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微生物学
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酶工程
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DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2024
·
IF 3.3
Yang Zhu,Guisheng Deng
The Cu(MeCN)4PF6-catalyzed reaction of 1-(2-hydroxyphenyl)-propargyl alcohols with aryl/alkyl mercaptan and subsequent treatment with K2CO3 only offered 3-(alkylthio)benzofurans, whereas the stoichiometric-exceeding CuI-mediated reaction and subsequent treatment with DIPEA furnished 2-(alkylthiomethyl)benzofurans with high selectivity. The amount of Cu(I) salts plays a key role in selective formation. This unique protocol for the selective construction of the two series of benzofurans containing alkylthio group proved to be suitable for broad substrates 1 and 2 except for aliphatic alkynyl alcohols.
研究领域:
有机化学
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药物化学
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DOI
PubMed
高影响因子
BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS
·
2019
·
IF 2.705
Qianwen Wang,Bingbing Ma,Shinya Fushinobu,Chunfang Zhang,Lian-Hua Xu
Cytochrome P450 enzymes (P450 or CYP) are some of the most versatile biocatalysts , and offer advantages for oxidizing unreactive C–H bonds in mild conditions. In this study, we identified a novel cytochrome P450 154C2 from Streptomyces avermitilis and characterized its function in 2α-hydroxylation of testosterone with regio- and stereoselectivity . To investigate the efficiency of electron transfer , we conducted biotransformation using two different P450 redox partners—RhFRED (RhF reductase domain) from Rhodococcus sp. and Pdx (putidaredoxin)/Pdr (putidaredoxin reductase) from Pseudomonas putida and revealed that RhFRED was more effective than Pdx/Pdr, especially in vivo . The K m and k cat values for testosterone were estimated to be 0.16 ± 0.05 mM and 0.13 ± 0.02 min −1 , and k cat / K m was 0.81 min −1 mM −1 . We also determined the crystal structure of the substrate-free form of CYP154C2 at 1.5 Å resolution. The structure has a closed conformation, and the substrate binding pocket is narrow, which can explain the strict substrate specificity of the enzyme .
研究领域:
生物化学
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酶学
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药物代谢
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DOI
PubMed
高影响因子
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
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2017
·Vol. 50
·期 9
·748-753
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IF 0.629
Zhaoyu Wang,Rongling Yang,Jizhong Wang,Yanhong Bi,Chun Zhu,Xiangjie Zhao,Linghong Nie,Wenqian Li
Regioselective enzymatic glycosylation of D-glucose and various structural alcohols for synthesizing β-D-glucopyranosides was successfully conducted. Among the β-glycosidases from seven potential plant seeds, the low-cost β-glycosidase from Prunus persica seed displayed excellent activity for salidroside preparation. Several crucial parameters, such as the solvent, buffer pH, buffer content, substrate molar ratio, enzyme dosage, and temperature were examined for yield optimization. Under the optimal conditions, the initial reaction rate and yield of salidroside were as high as 3.04 mM/h and 18.90%, respectively. Moreover, the alcohol acceptor recognition of the enzyme in synthesizing β-D-glucopyranosides was also investigated. The experimental data indicated that β-glycosidase activity and yield varied widely among all the tested alcohols due to the specific spatial structures of various acceptors.
研究领域:
生物化学
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酶工程
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DOI
高影响因子
Molecular Catalysis
·
2022
·
IF 5.089
Yunjian Ma,Hongjing Liang,Zexin Zhao,Bin Wu,Dongming Lan,Frank Hollmann,Yonghua Wang
Unspecific peroxygenases (UPOs, EC 1.11.2.1) are promising oxyfunctionalization catalysts because of their unique stereoselectivity. However, so far only a few UPOs have been reported. In this study, gene mining was used to identify a gene from Galerina marginata that coded for a novel UPO ( Gma UPO). Gma UPO was expressed in Pichia pastoris X-33 by scale-up fermentation (the UPO activity of the culture supernatant was 118 U/L). Gma UPO exhibited a molecular weight of 40 kDa and exhibited highest activity at 35°C and pH 9, respectively. Furthermore, Gma UPO was demonstrated to catalyze the epoxidation, sulfoxidation, and hydroxylation of common substrates, particularly fatty acids such as tridecanoic acid. The molecular basis for Gma UPO regioselectivity for fatty acid hydroxylation was explored by molecular modelling. The regioselectivity was mostly governed by the architecture of the enzyme's active site.
研究领域:
生物化学
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酶工程
·
微生物学
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2017
·
IF 4.339
Yuqing Wang,Li Yan,Cunyao Li,Miao Jiang,Wenlong Wang,Yunjie Ding
Porous organic copolymer (denoted as CPOL-BP&P) was afforded through the copolymerization of vinyl biphephos and tris (4-vinylphenyl)phosphine monomers under solvothermal conditions, and followed with impregnation method provided a highly efficient Rh/CPOL-BP&P catalyst with high activity (TOF = 11,200 h −1 ) and regioselectivity (the ratio of linear to branched aldehydes, l:b = 62.2) for heterogeneous hydroformylation of 1-butene. High regioselectivity was also obtained in the hydroformylation of butene mixture (2-butene: l:b = 55.8, isomeric mixture of butenes: l:b = 56.0). The Rh/CPOL-BP&P catalysts were thoroughly characterized by means of nitrogen sorption isotherms, in situ FT-IR, XPS, solid-state 31 P MAS NMR, HAADF-STEM, SEM and TEM. The formation of unique coordination bonds with Rh species in the polymer skeleton was determined. Heterogeneous hydroformylation of butenes was effectively realized due to a synergetic effect between PPh 3 moiety and biphephos moiety.
研究领域:
材料化学
·
催化化学
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DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2020
·
IF 4.335
Ling Tang,Qin Yang,Jianfang Zhang,Guisheng Deng
A regioselective reverse strategy for the construction of eight-membered sulfur-containing heterocycle-fused γ-pyrones and 2-(1,4-dithianyl)-4-pyrones starting from 2-diazo-γ-pyrones and dithioacetals was achieved for the first time. The process combines C–S bond formation via sulfur ylides and C–C bond formation via electron transfer to afford the target molecules in a facile manner with 100% regioselectivity and in excellent isolated yields (up to 90%).
研究领域:
有机化学
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合成化学
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DOI
高影响因子
Food Bioscience
·
2024
·
IF 4.8
Dami Li,Yaoyao Zhang,Xing Qiao,Hira Ijaz,Shangde Sun
Resveratrol (RES) is a natural non-flavonoid polyphenolic antioxidant. The low solubility of RES in water (26 mg/L) and oil (175.51 mg/kg) limited its antioxidant activity and bioavailability. In order to overcome these issues, in this work, a lipophilic resveratrol laurate was efficiently synthesized using RES as starting material in the presence of enzymes. The catalytic activities of enzymes (Lipase CALA, Lipozyme TL 100L, Lipase CALB, Novozym 435, Lipozyme TLIM, and Lipozyme RMIM) were investigated and screened. Moreover, reaction conditions were optimized using response surface methodology. Meanwhile, thermodynamic and kinetic analyses were also conducted to investigate the enzymatic mechanism. Results showed that, Lipozyme RMIM showed the best performance for resveratrol monolaurates regioselective synthesis. Two products, 3-resveratrol monolaurate (3-RC12) and 4′-RC12, were prepared and purified. The optimal reaction conditions for the preparation of 3-RC12, and 4′-RC12 were 1:65 substrate ratio and 11.7 wt% lipase dosage at 75 °C for 33.2 h. Under these conditions, the RES conversion reached a maximum of 98.04 ± 1.76%. The regioselective products were analyzed for antioxidant activity. Notably, the esterification site significantly impacts resveratrol monoesters' antioxidant activity. And 3-RC12 demonstrates superior ABTS and DPPH radical cation scavenging activity, surpassing RES and 4′-RC12. Notably, in yield and antioxidant activity, 3-RC12 is better than 4′-RC12, which make it a potential antioxidant for industrial application.
研究领域:
食品科学
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生物化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）