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
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.
[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 by ring size[J]. J Am Chem Soc, 2007, 129:7393-7398.
[22] HILKER I, RABANI G, VERZIJL G K M, et al. Chiral polyesters by dynamic kinetic resolution polymerization[J]. Angew Chem Int Ed, 2006, 45:2130-2132.
2018, Vol. 45 
