BIOPROCESS AND BIOSYSTEMS ENGINEERING
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2022
·Vol. 46
·期 2
·171-181
·
IF 3.434
Zhang Yin-Jun,Wei Li-Tian,Zhou Ming-Peng,Wei Chun,Yu Xin-Jun
( R )-N-(2,6-dimethylphenyl) aminopropionic acid methyl ester (( R )-DMPM) is an important chiral intermediate of the fungicide N-(2,6-Dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester (( R )-Metalaxyl). In this study, (1) D3520 (macroporous acrylic anion resin), selected from the ten resins, was used to immobilize the esterase from Pseudochrobactrum asaccharolyticum WZZ003 (PAE07) for resoluting the ( R,S )-DMPM to obtain ( R )-DMPM. (2) Up to 20 g/L PAE07 could be immobilized onto D3520 with a high enzymatic activity of 32.4 U/g. Moreover, the Km and Vmax values of 19.1 mM and 2.8 mM/min for D3520-immobilized PAE07 indicated its high activity and stereoselectivity. (3) The optimal temperature and pH for the immobilized PAE07 were 40 ℃ and 8.0, and substrate concentration was up to 0.35 M. After 15 h reaction, the conversion rate from ( R,S )-DMPM to ( R )-DMPM was 48.0% and the e.e.p and E values were 99.5% and 1393.0, respectively. In scale-up resolution, 200 g/L substrate and 12.5 g immobilized esterase PAE07 condition, a conversion rate from substrate to product of 48.1% and a product e.e.p of 98% were obtained within 12 h, with the activity of immobilized PAE07 retained 80.2% after 5 cycles of reactions. These results indicated that the D3520-immobilized esterase PAE07 had great potential for enzymatic resolution of ( R,S )-DMPM to prepare ( R )-Metalaxyl.
研究领域:
生物化学
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酶工程
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有机合成
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产品关联
DOI
PubMed
高影响因子
BIOCATALYSIS AND BIOTRANSFORMATION
·
2019
·
IF 1.627
Lu Dong,Yongkai Xu,Yun Zhang,Aijun Sun,Yunfeng Hu
Chiral 1-phenylethanol and its ester derivative are important chiral chemicals in diverse industries and the preparation of those optically pure enantiomers is of great importance. One bacterium, Bacillus sp. DL-2, whose extracellular proteases could efficiently asymmetrically hydrolyse (±)-1-phenylethyl acetate, was isolated from the deep sea of the Western Pacific. After the immobilization of extracellular proteases and the optimization of enzymatic reactions, (R)-1-phenylethanol was prepared with the enantiomeric excess (e.e.) being 97% and the yield being 41%, respectively. The optimal resolution reaction condition for the preparation of (R)-1-phenylethanol using immobilized extracellular proteases was found to be 5-mM (±)-1-phenylethyl acetate, 360 mg/mL immobilized extracellular proteases, pH 6.5, and 20 °C for 2 h. (S)-1-phenylethyl acetate was generated through enzymatic kinetic resolution with the e.e. being as high as 99% and the yield being 71%, respectively. The optimal resolution reaction condition for the preparation of (S)-1-phenylethyl acetate was found to be 2.5-mM (±)-1-phenylethyl acetate, 440 mg/mL immobilized extracellular proteases, pH 7.5, and 35 °C for 10 h. Our report is the first report about the kinetic resolution of (±)-1-phenylethyl acetate using proteases and the enantio-preference of the proteases was found to be the same as those of most other esterases/lipases. Also notably, the optical purity of (S)-1-phenylethyl acetate generated through kinetic resolution using the proteases of Bacillus sp. DL-2 was the highest report so far. Proteases from deep-sea Bacillus sp. DL-2 are new contributions to the biocatalyst library for the preparation of valuable chiral alcohols and chiral esters through kinetic resolution.
研究领域:
生物催化
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生物化学
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微生物学
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手性化学
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产品关联
DOI
高影响因子
MOLECULES
·
2019
·Vol. 24
·期 3
·490
·
IF 3.06
Xiu Xing,Jun-Qi Jia,Jing-Fan Zhang,Zi-Wen Zhou,Jun Li,Na Wang,Xiao-Qi Yu
In this study, an immobilization strategy for magnetic cross-linking enzyme aggregates of lipase B fromCandida antarctica(CALB) was developed and investigated. Magnetic particles were prepared by conventional co-precipitation. The magnetic nanoparticles were modified with 3-aminopropyltriethoxysilane (APTES) to obtain surface amino-functionalized magnetic nanoparticles (APTES–Fe3O4) as immobilization materials. Glutaraldehyde was used as a crosslinker to covalently bind CALB to APTES–Fe3O4. The optimal conditions of immobilization of lipase and resolution of racemic 1-phenylethanol were investigated. Under optimal conditions, esters could be obtained with conversion of 50%, enantiomeric excess of product (eep) > 99%, enantiomeric excess of substrate (ees) > 99%, and enantiomeric ratio (E) > 1000. The magnetic CALB CLEAs were successfully used for enzymatic kinetic resolution of fifteen secondary alcohols. Compared with Novozym 435, the magnetic CALB CLEAs exhibited a better enantioselectivity for most substrates. The conversion was still greater than 49% after the magnetic CALB CLEAs had been reused 10 times in a 48 h reaction cycle; both eesand eepwere close to 99%. Furthermore, there was little decrease in catalytic activity and enantioselectivity after being stored at −20 °C for 90 days.Keywords:CALB;magnetic nanoparticles;cross-linked enzyme aggregates;resolution;secondary alcohols
研究领域:
生物化学
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材料科学
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酶工程
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产品关联
DOI
PubMed
高影响因子
KOREAN JOURNAL OF CHEMICAL ENGINEERING
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2019
·Vol. 36
·期 5
·729-739
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IF 2.476
Pan Jiaying,Ou Zhimin,Tang Lan,Shi Hanbing
Racemic 1-phenylethylamine was resolved by enantiomer selective acetylation using Fe 3 O 4 -chitosan microsphere (CTS)-glutaraldehyde-lipase in a solvent-free system under an alternating magnetic field. Magnetic chitosan microspheres (Fe 3 O 4 -CTS) were prepared via chemical co-precipitation and cross-linked with lipase using glutaraldehyde to form Fe 3 O 4 -CTS-glutaraldehyde-lipase particles. The magnetic, physicochemical, and textural characteristics of Fe 3 O 4 -CTS-glutaraldehyde-lipase particles were assessed by Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The optimal immobilization conditions were 2.4 mg/mL lipase, 10 mg/mL Fe 3 O 4 -CTS-glutaraldehyde, pH 8.5, 35 °C, 3 h. The loading amount of lipase and the specific activity got to 132 mg/g carrier and 48 U/g. The optimal reaction conditions of the acylation reaction using Fe 3 O 4 -CTS-glutaraldehyde-lipase were 300 mmol/L 1-phenylethylamine, 150 mg immobilized lipase, 2 mL vinyl acetate, 12.6 ×g rotating speed, 40 °C, 8 h. The activity of the Fe 3 O 4 -CTS-glutaraldehyde-lipase particles and conversion were improved when they were exposed to an external alternating magnetic field. The optimum magnetic field was 12 Gs (500 Hz). The conversion, enantiomeric excess of ( R )- N -(1-phenylethyl)acetamide, and E value reached 41.8%, 98.4%, and 264, respectively. Fe 3 O 4 -CTS-glutaraldehyde-lipase could be reused seven times. A kinetic model of the immobilized lipase-catalyzed resolution of 1-phenylethylamine was set up based on the ping-pong bi-bi mechanism. The kinetic constants were V max =1.62×10 −2 mM/min, K A =2.84×10 −4 mM, and K B =5.8×10 −1 mM. The model data fit well with the experimental data.
研究领域:
生物化学
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材料科学
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催化工程
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS B-ENZYMATIC
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2013
·
IF 2.823
Jian-Yong Zheng,Jia-Yu Wu,Yin-Jun Zhang,Zhao Wang
The mycelium of Aspergillus oryzae WZ007 was successfully developed to kinetic resolution of ( R , S )-ethyl-2-(4-hydroxyphenoxy) propanoate (( R , S )-EHPP) for production of ( R )-ethyl-2-(4-hydroxyphenoxy) propanoate (( R )-EHPP). The key biocatalytic process parameters (pH, temperature, rotation speed and substrate concentration) were optimized. Under the optimum conditions, the optical purity of ( R )-EHPP was improved up to >99% when the conversion was above 49%. A. oryzae WZ007 whole-cell lipase exhibited high reaction capacity, enantioselectivity and good reusability. The tolerable substrate concentration was 0.5 mol/L, and dry mycelium of A. oryzae WZ007 maintains over 80% of its initial activity after eight repeating cycles. Therefore the enzymatic preparation of ( R )-EHPP route was suitable for industrial application.
研究领域:
生物化学
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微生物学
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制药工程
✓ 已验证
产品关联
DOI
高影响因子
ENZYME AND MICROBIAL TECHNOLOGY
·
2014
·
IF 2.966
Chuan-Yang Shang,Wei-Xun Li,Rui-Feng Zhang
ZnO nanowires were successfully introduced into a macroporous SiO 2 by in situ hydrothermal growth in 3D pores. The obtained composites were characterized by SEM and XRD, and used as supports to immobilize Candida antarctica lipase B (CALB) through adsorption. The high specific surface area (233 m 2 /g) and strong electrostatic interaction resulted that the average loading amount of the composite supports (196.8 mg/g) was 3–4 times of that of macroporous SiO 2 and approximate to that of a silica-based mesoporous material. Both adsorption capacity and the activity of the CALB immobilized on the composite supports almost kept unchanged as the samples were soaked in buffer solution for 48 h. The chiral resolution of 2-octanol was catalyzed by immobilized CALB. A maximum molar conversion of 49.1% was achieved with 99% enantiomeric excess of ( R )-2-octanol acetate under the optimal condition: a reaction using 1.0 mol/L ( R , S )-2-octanol, 2.0 mol/L vinyl acetate and 4.0 wt.% water content at 60 °C for 8 h. After fifteen recycles the immobilized lipase could retain 96.9% of relative activity and 93.8% of relative enantioselectivity .
研究领域:
生物化学
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材料科学
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催化工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ENZYME AND MICROBIAL TECHNOLOGY
·
2017
·
IF 2.502
Kun Zhang,Zhiyou Pan,Zhoujian Diao,Shuli Liang,Shuangyan Han,Suiping Zheng,Ying Lin
Kinetic resolution of sec -alcohols is a green process with biocatalyst. Candida antarctica lipase B (CALB) displayed on Pichia pastoris cell-surface (Pp-CALB) was characterized in kinetic resolution of sec -alcohols with different structures. The reaction parameters including acyl donors, molar ratio of substrates, solvents and temperatures were examined with 2-octanol as model substrate. 47.4% molar conversion of 2-octanol and 99.7% ee p were obtained after a 5 h reaction with Pp-CALB, and 90% of its original activity still remained after being reused for 10 cycles. Pp-CALB was then used to several sec -alcohols and it showed great enzymatic activity and enantioselectivity to all tested sec -alcohols, more than 93.1% of ee p . The enantioselective characteristics of Pp-CALB catalysed sec -alcohols with different structures were compared with Novozyme 435 which was almost the same. Solvent free system as one way of green chemistry was applied to Pp-CALB and Pp-CALB showed great catalytic activity and enantioselectivity. Pp-CALB was potential biocatalyst of high enzymatic activity and enantioselectivity using in resolution of sec -alcohols.
研究领域:
生物化学
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酶工程
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绿色化学
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产品关联
DOI
PubMed
高影响因子
CATALYSIS COMMUNICATIONS
·
2019
·
IF 3.674
Yuanmei Wen,Liaotian Peng,Yang Zhou,Tao Peng,Yu Chen,Xiaoling Cheng,Yongzheng Chen,Jiawei Yang
Here we report a methionine sulfoxide reductase B (MsrB) enzymatic system for the preparation of ( S )-sulfoxides through kinetic resolution of racemic ( rac ) sulfoxides. Eight MsrB homologue recombinant proteins were expressed and their activities on asymmetric reduction of rac -sulfoxides were analyzed. Among these MsrB homologue proteins, one protein from Acidovorax species showed good activity and enantioselectivity towards several aryl-alkyl sulfoxides. The ( S )-sulfoxides were prepared with 93–98% enantiomeric excess through kinetic resolution at initial substrate concentration up to 50 mM. The establishment of MsrB catalytic kinetic resolution system provides a new efficient green strategy for preparation of ( S )-sulfoxides.
研究领域:
生物化学
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合成生物学
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绿色化学
✓ 已验证
DOI
高影响因子
MICROCHIMICA ACTA
·
2021
·Vol. 188
·期 9
·1-10
·
IF 5.833
Guo Ping,Yuan Bao-Yan,Yu Yun-Yan,Zhang Jun-Hui,Wang Bang-Jin,Xie Sheng-Ming,Yuan Li-Ming
The fascinating framework structures and unique properties of chiral covalent organic frameworks (COFs) make them promising candidates as novel separation medium for high-performance liquid chromatography (HPLC). However, the irregular morphology, inhomogeneous particle size, and low density of conventional COF particles will lead to a low column efficiency, undesirable chromatographic peak shape, and high column backpressure of such COF-packed columns. In this work, a chiral COF CTpBD was synthesized by the Schiff base reaction between benzidine (BD) and chiral organic monomer CTp obtained through the reaction of 1,3,5-triformylphoroglucinol (Tp) and (+)-diacetyl-L-tartaric anhydride ((+)-Ac-L-Ta). The chiral COF CTpBD was immobilized on the surface of amino functionalized silica (SiO 2 -NH 2 ) by an in situ growth approach to prepare the chiral COF core-shell microsphere composite CTpBD@SiO 2 , which was used as a novel chiral stationary phase (CSP) for HPLC enantioseparation. Various kinds of racemates were separated on the CTpBD@SiO 2 -packed column with a low column backpressure (8–11 bar). Some effects such as the analyte mass and column temperature on the HPLC enantioseparation have been studied in detail. The fabricated CTpBD@SiO 2 -packed column exhibited high column efficiency (e.g., 16,800 plates m −1 for atenolol), high enantioselectivity, and good reproducibility toward various racemates. The highest resolution value, retention factor, and separation factor reach to 2.11, 2.85, and 3.73, respectively. The relative standard deviations (RSD) of peak area, peak height, half-peak width, and retention time of atenolol were all below 3.0%. Graphical abstract
研究领域:
分析化学
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色谱技术
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产品关联
DOI
PubMed
高影响因子
MOLECULES
·
2023
·Vol. 28
·期 3
·922
·
IF 4.6
Pengcheng Li,Jingjing Zhu,Hongyu Zhang,Lan Wang,Shulin Wang,Mengting Zhang,Jianping Wu,Lirong Yang,Gang Xu
Chiral amines are essential components for many pharmaceuticals and agrochemicals. However, the difficulty in obtaining enantiomerically pure amines limits their application. In this study, hollow amorphous ZIF-90 (HamZIF-90) materials were prepared by template engraving, and chemical–enzyme coupling catalysts (HamZIF-90@Pd@CALB) were constructed for the chiral resolution of 1-phenylethylamine. Different from conventional materials, HamZIF-90 had tunable hollow structures by altering its central node zinc ion concentrations, and the embedded hydrogel template gave it more pore structures, which facilitated the loading of enzyme molecules and Pd nanoparticles (NPs). The establishment of the coupling catalysts shortened the mass transfer distance of the reactant molecules between the metal nanoparticles and the enzyme catalyst in the dynamic kinetic resolution (DKR) reaction, resulting in 98% conversion of 1-phenylethylamine and 93% selectivity of Sel.R-amide. The proposal of this idea provided a good idea for future tailor-made MOFs loaded with chemical and enzyme coupled catalyst.Keywords:hollow amorphous;HamZIF-90@Pd@CALB;DKR;1-phenylethylamine
研究领域:
化学
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生物催化
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Sen Xu,Meng Wang,Bo Feng,Xinchen Han,Zijie Lan,Huajun Gu,Hexing Li,Hui Li
Dynamic kinetic resolution (DKR) of amines is an important strategy for the synthesis of chiral drugs and their building blocks; however, improving the matchability of metal-catalyzed racemization and enzymatic resolution is still a task. In this paper, Pd nanoparticles (NPs) were encapsulated inside the cages of ethylenediamine-grafted MIL-101 (ED-MIL-101), giving highly efficient catalysts (Pd/ED-MIL-101) for the racemization of primary amines. The racemization can be combined with lipase-catalyzed resolution in a one-pot DKR of rac -1-phenylethylamine leading to optically pure product (>99% ee value) with an excellent conversion and selectivity up to 99% and 93%, respectively, superior to other catalysts, such as Pd/MIL-101, Pd/MCM-41 and commercially available Pd/C. Furthermore, the heterogeneous chemoenzymatic catalyst combination can be recovered and recycled 8 times without significant loss of efficiency. The enhance catalytic performances were found to depend on the amine modification of MIL-101 that not only endows the surface of its cages with basic property, but also enables efficiently confining Pd NPs in the cages. In addition, the matchability of such chemoenzymatic catalyst combination can be further enhanced by conducting the DKR process under microwave irradiation.
研究领域:
化学
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生物催化
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材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
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2013
·Vol. 51
·期 9
·2049-2057
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IF 3.543
Xueqi Qian,Zhengyang Jiang,Xianfu Lin,Qi Wu
Amphiphilic poly(amine-co-ester)s, which contain a single effective enantiomer of an asymmetric drug and thus can avoid potentially serious side effects, are difficult to prepare through nonselective chemical routes not only in the process of introducing chiral drugs to the polymer, but also in the synthesis of the polymer's backbone by metal catalysts. A model of racemic mexiletine, an important antiarrhythmic agent, was used to demonstrate the tandem combination of Candida antarctica lipase B (CAL-B)- and Pd/C-catalyzed dynamic kinetic resolution (DKR) and subsequent CAL-B-catalyzed polycondensation, as an efficient protocol to prepare poly(ethylene glycol)-functionalized poly(amine-co-ester)s containing (R)-mexiletine with 99% ee value. Chemoenzymatic DKR and enzymatic polymerization conditions were optimized, and the optical purity of incorporated (R)-mexiletine was confirmed through its hydrolysis from polyester. The copolymers can readily self-assemble into nanometer-scale-sized micelles with well-dispersed spheres, which have a size distribution that can be efficiently adjusted by changing the polymer concentration. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013
研究领域:
生物化学
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制药工程
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高分子化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）