Please wait a minute...
浙江大学学报(理学版)  2018, Vol. 45 Issue (1): 112-117    DOI: 10.3785/j.issn.1008-9497.2018.01.016
化学     
脂肪酶催化合成聚R-3-羟基丁酸乙酯寡聚物研究
夏波1, 吴起2
1. 浙江农林大学暨阳学院, 浙江 诸暨 311800;
2. 浙江大学 化学系, 浙江 杭州 310027
Lipase-catalyzed synthesis of R-Poly (3-hydroxybutyrate) oligomer
XIA Bo1, WU Qi2
1. Jiyang College of Zhejiang A & F University, Zhuji 311800, Zhejiang Province, China;
2. Department of Chemistry, Zhejiang University, Hangzhou 310027, China
 全文: PDF(1296 KB)   HTML  
摘要: 聚R-3-羟基丁酸酯是一类具有重要生理作用的聚合物,其合成方法一直是手性聚合物合成领域的研究热点之一.在充分考察底物构型、溶剂等因素对酶促动力学拆分/聚合反应影响的基础上,结合过渡金属配合物对醇的原位外消旋化作用与酶促聚合反应,建立了一种绿色、高效的酶促动态动力学拆分/聚合一锅合成聚R-3-羟基丁酸酯的方法.通过该方法制备所得聚合物的分子量可以达到2.0×103 Da.通过改变聚合单体的光学纯度还可实现对聚合物分子量的调控,在不同光学纯度聚合单体的聚合反应中,聚合物的分子量可以较为均匀地分布在0.3×103~1.3×103 Da内.该方法具有高效、无毒等优点,对进一步研究手性聚酯的应用具有重要的理论和现实意义.
关键词: 酶促聚合立体选择性缩合手性聚酯分子量调控    
Abstract: R-poly (3-hydroxybutyrate) is an important organic polymer with significant physiological effects and its synthesis is always the focus of polymer chemistry. Herein, we report a new strategy for the synthesis of poly (R-3-hydroxyl) butyrate. In this strategy, high molecular weight chiral polyester is obtained through lipase-catalyzed stereo-selective condensation of rac-ethyl-3-hydroxyl-butyrate, and the highest molecular weight can reach to 2.0×103 Da. The successful combination of enzyme-catalyzed dynamic kinetic resolution and enzyme-catalyzed condensation makes this strategy more efficient. Moreover, the adjusting of molecular weight has also been done by changing the optical purity value of monomer. The molecular weight of the obtained chiral polymer can be uniformly distributed within 0.3×103 to 1.3×103 Da.
Key words: lipase-catalyzed polymerization    stereo-selective condensation    chiral polyester    molecular weight adjusting
收稿日期: 2017-05-31 出版日期: 2017-12-15
CLC:  O631.5  
基金资助: 浙江省自然科学基金资助项目(LY17B040002);浙江农林大学暨阳学院人才启动基金项目(JY2015RC009).
作者简介: 夏波(1981-),ORCID:http://orcid.org/0000-0002-7791-2636,男,博士,讲师,主要从事手性聚合物合成及生物催化研究,E-mail:bobohao424@126.com.
服务  
把本文推荐给朋友
加入引用管理器
E-mail Alert
RSS
作者相关文章  
夏波
吴起

引用本文:

夏波, 吴起. 脂肪酶催化合成聚R-3-羟基丁酸乙酯寡聚物研究[J]. 浙江大学学报(理学版), 2018, 45(1): 112-117.

XIA Bo, WU Qi. Lipase-catalyzed synthesis of R-Poly (3-hydroxybutyrate) oligomer. Journal of ZheJIang University(Science Edition), 2018, 45(1): 112-117.

链接本文:

https://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2018.01.016        https://www.zjujournals.com/sci/CN/Y2018/V45/I1/112

[1] POULHES F, MOUYSSET D, GIL G, et al. Novozym 435-catalyzed synthesis of polyetherimides from amino-esters, or diesters and diamines built on ethylene-and diethylene-glycol moieties[J]. Polymer, 2012, 53:1172-1179.
[2] XU F L, ZHONG J R, QIAN X Q,et al. Multifunctional poly(amine-ester)-type hyperbranched polymers:Lipase-catalyzed green synthesis, characterization, biocompatibility, drug loading and anticancer activity[J]. Polym Chem, 2013(4):3480-3490.
[3] YAMAGUCHI S, TANHA M, HULT A,et al. Green polymer chemistry:lipase-catalyzed synthesis of bio-based reactive polyesters employing itaconic anhydride as a renewable monomer[J]. Polymer Journal, 2014, 46:2-13.
[4] INPRAKHON P, PANLAWAN P, PONGTHARANKUL T, et al. Toward one-pot lipase-catalyzed synthesis of poly (ε-caprolactone) particles in aqueous dispersion[J]. Colloids and Surfaces B:Biointerfaces, 2014, 113:254-260.
[5] JIANG Z Z, ZHANG J W. Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactide with diesters and diols[J]. Polymer, 2013, 54:6105.
[6] ZHAO X Y, SUN L, WANG M Z,et al. Review of crosslinked and non-crosslinked copolyesters for tissue engineering and drug delivery[J]. Polym Int, 2014, 63:393-401.
[7] MA J P, PANG Y, WANG M,et al. The copolymerization reactivity of diols with 2, 5-furandicarboxylic acid for furan-based copolyester materials[J]. J Mater Chem, 2012, 22:3457-3461.
[8] REUSCH R N. Biological complexes of poly-β-hydroxybutyrate[J]. FEMS Microhiol Rev, 1992, 103:119-130.
[9] NAVES A F, FERNANDES H T C, IMMICH A P S, et al. Enzymatic syntheses of unsaturated polyesters based on isosorbide and isomannide[J]. Journal of Polymer Science, Part A:Polymer Chemistry, 2013, 51:3881-3891.
[10] KELLER A. CORRIGENDUM:Polymer crystals[J]. Reports on Progress in Physics, 1969, 32(2):769.
[11] WELLAND E J, STEJNY J, HALTER A,et al. Selective degradation of chain folded single crystals of poly (β-hydroxybutyrate)[J]. Polym Commun, 1989, 30:302-304.
[12] SEEBACH D, BRUNNER A, BURGER H M,et al. Isolation and 1H-NMR spectroscopic identification of poly (3-Hydroxybutanoate) from Prokaryotic and Eukaryotic organisms[J]. Eur J Biochem, 1994, 224:317-328.
[13] POOL R. The periaqueductal gray matter mediates opiate-induced immunosuppression[J]. Science, 1989, 245:188-190.
[14] JEDLIN'SKI Z, KURCOK P, LENZ R W. First facile synthesis of biomimetic poly-(R)-3-hydroxybutyrate via regioselective anionic polymerization of (S)-β-butyrolactone[J]. Macromolecules, 1998, 31:6718-6720.
[15] JEDLIN'SKI Z, KURCOK P, ADAMUS G, et al. Biomimetic polyesters and their role in ion transport across cell membranes[J]. Acta Biochim Pol, 2000, 47:79-85.
[16] JEDLIN'SKI Z, ADAMUS G, KOWALCZUK SCHUBERT M R, et al. Electrospray tandem mass spectrometry of poly (3-hydroxybutanoic acid) end groups analysis and fragmentation mechanism[J]. Rapid Commun Mass Spectrom, 1998, 12:357-360.
[17] SEEBACH D, BVRGER H M, MVLLER H M, et al. Synthesis of linear oligomers of (R)-3-hydroxybutyrate and solid-state structural investigations by electron microscopy and X-ray scattering[J]. Helv Chim Acta, 1994, 77:1099-1123.
[18] LENGWEILER U D, FRITZ M G, SEEBACH D. Synthase monodisperser linearer und cyclischer oligomere der (R)-3-hydroxybuttersäure mit bis zu 128 Einheiten[J]. Helv Chim Acta, 1996, 79:670-701.
[19] BACHMANN B M, SEEBACH D. Synthesis and structure of linear and cyclic oligomers of 3-hydroxybutanoic acid with specific sequences of (R)-and (S)-configurations[J]. Helv Chim Acta, 1998, 81:2430-2461.
[20] BUIJTENEN J V, MEULDIJK J, PALMANS A R A, et al. Chiral polymers by iterative tandem catalysis[J]. Chem Commun, 2006, 30:3169-3171.
[21] BUIJTENEN J, VERBRUGGEN M, ROUMEN L, et al. Switching from S-to R-selectivity in the Candida antarctica Lipase B-catalyzed ring-opening of ω-methylated lactones:Tuning polymerizations b
No related articles found!