Chemoenzymatic synthesis poly

Poly(malic acid) is a biodegradable and bioadsorbable water-soluble polyester having a carboxylic acid in the side chain. The chemoenzymatic synthesis of poly(malic acid) was achieved by the lipase-catalyzed polymerization of benzyl (3-malolactonate, followed by the debenzylation. The molecular weight of poly(benzyl (3-malolactonate) increased on copolymerizafion with a small amount of (3-PL using lipase CR catalyst. ... 

Chemoenzymatic synthesis of biodegradable poly(malic acid) was performed by lipase-catalyzed polymerization of benzyl /J-malolactone, followed by the debenzylation [72]. The addition of a small amount of /J-PL (17 mol % for the monomer) increased Mw up to 3 x 104 [73]. 

Following route A (Fig. 1), Yan Xiao et al. reported the chemoenzymatic synthesis of poly(8-caprolactone) (PCL) and chiral poly(4-methyl-8-caprolactone) (PMCL) microparticles [5]. The telechelic polymer diol precursors were obtained by enzymatic polymerization of the corresponding monomers in the presence of hexanediol. Enzymatic kinetic resolution polymerization directly yielded the (R)-and (S )-enriched chiral polymers. After acrylation using acryloylchloride, the chiral and nonchiral particles were obtained by crosslinking in an oil-in-water emulsion photopolymerization. Preliminary degradation experiments showed that the stereoselectivity of CALB is retained in the degradation of the chiral microparticles (Fig. 2). 

Scheme 2 Chemoenzymatic synthesis of block copolymers consisting of a semifluorinated block of poly(l//, IH, 2H, 2//-perfluorooctyl metharylate) and PCL [29]...

X. Chen, A. Johnson, J. S. Dordick, and D. G. Rethwisch, Chemoenzymatic synthesis of linear poly(sucrose acrylate) Optimization of enzyme activity and polymerization conditions, Macromol. Chem. Phys., 195 (1994) 3567-3578. 

Vasiliu D, Razi N, Zhang Y, Jacobsen N, AlUn K, Liu X, Hoffmann J, Bohorov O, BUxt O. Large-scale chemoenzymatic synthesis of blood group and mmor-associated poly-N-acetyllactos-amine antigens. Carbohydr. Res. 2006 341 1447-1457. 

Totani K, Kubota T, Kuroda T, Murata T, Hidari Kl, Suzuki T, Suzuki Y, Kobayashi K, Ashida H, Yamamoto K, Usui T. Chemoenzymatic synthesis and application of glycopolymers containing multivalent sialyloligosaccharides with a poly(L-glutamic acid) backbone for inhibition of infection by influenza viruses. Glycobiology 2003 13 315-326. 

A polynucleoside with an unnatural polymeric backbone was synthesized by SBP-catalyzed oxidative polymerization of thymidine 5 -p-hydroxyphenylacetate [59]. Chemoenzymatic synthesis of a new class of poly(amino acid), poly(tyrosine) containing no peptide bonds, was achieved by the peroxidase-catalyzed oxidative polymerization of tyrosine ethyl esters, followed by alkaline hydrolysis [60]. 

Wyatt, M.F., Duxbury, C.J., Thurecht, K.J., and Howdle, S.M. (2006) One-Step Chemoenzymatic synthesis of poly(e-caprolactone-block-methyl methacrylate) in supercritical C02. Macromolecules, 39 (16), 5352-5358. 

Albeitin L, Kohleit C, Stenzel M, Foster LJR, Davis TP (2004) Chemoenzymatic synthesis of narrow-polydispersity glycopolymers poly(6-0-vinyladipoly-D-glucopyranose). Biomacromolecules 5(2) 255-260... 

Bear, M.M., Gammas, S., Langlois, V., and Guerin, Ph., 1997, Chemoenzymatic synthesis of poly( (2R,3S)-benzyl-p-3-methyl malate) 3- methylaspartase as a versatile enzyme in the praparatio of the chiral precursor. C. R. Acad. Scl Paris 325 (Ilb) 165-172. 

Donati, I., Paoletti, S., 2009. Material properties of alginates. Alginates Biol. Appl. 13, 1—53. Dossi, M., Storti, G., MoscateUi, D., 2010. Synthesis of poly(alkyl cyanoacrylates) as biodegradable polymers for dmg delivery applications. Macromol. Symposia 289, 124—128. Ferreira, L., Rafael, A., Lamghari, M., Barbosa, M.A., Gil, M.H., Cabrita, A.M., Dordick, J.S., 2004. Biocompatibihty of chemoenzymatically derived dextran-acrylate hydrogels. J. Biomed. Mater. Res. A 68, 584—596. 

However, all synthetic approaches involving ATRP rely on a metal catalyst. Full metal-free and thus greener approaches to block copolymers were realized by the combination of Upase ROP with nitroxide-mediated living free radical polymerization [44]. With this system it was also possible to successfully perform a one-pot chemoenzymatic cascade polymerization from a mixture containing a dual initiator, CL and styrene (Fig. 12). Moreover, it was shown that this approach is compatible with the stereoselective polymerization of 4-methylcaprolactone for the synthesis of chiral block copolymers. A metal-free synthesis of block copolymers using a radical chain transfer agent as a dual initiator in enzymatic ROP to yield poly(CL-f -styrene) was also reported recently [119]. 

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