Adv Polym Sci (2010) 237: 21– 54 DOI:10.1007/12_2010_73 c Springer- V erlag Berlin Heidelber g 2010 Published online: 28 May 2010 Transferases in Polymer Chemistry Jeroen van der Vlist and Katja Loos Abstract Transferases are enzymes that catalyze reactions in which a group is tr ansf er red from onecompou nd to ano ther . Thi s make s thes e enz yme s ideal cata lysts for poly mer iza tion rea cti ons. In nature , tra nsf erases are res pons ibl e for the synt hes is of many import ant natura l macromol ecule s. In s ynthet ic polymer chemis try , vari ous transf erase s are used to synthe size polymers in vitro. This chapter revie ws some of these approaches, such as the enzymatic polymerization of polyesters, polysaccha- rides, and polyisoprene. Keywords Biocatalysis · Enzymatic polymeri zati on · Polyester · Polyisoprene · Polysaccharide · Transferase Contents 1 In tr oduc tio n .................................................................................... 23 2 Ac ylt ra nsf erases (EC 2.3 ) ..................................................................... 24 2.1 Polyester Synt ha se ..................................................................... 24 2.2 Tr ansgl uta minase ....................................................................... 27 3 Gly cos ylt ran sferases (EC 2.4 ) ................................................................ 28 3. 1 Phos ph or yl as e .......................................................................... 29 3. 2 Br an ch ing Enzy mes .................................................................... 38 3. 3 Glu cansuc ra ses ......................................................................... 40 3. 4 Le vansu cr ase ........................................................................... 40 3. 5 Amylomal ta se .......................................................................... 40 3.6 Hya lur ona n Syn tha se ................................................................... 41 J. van der Vlist and K. Loos ( ) Department of Polymer Chemistry and Zernike Institute for Advanced Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747AG Groningen, The Netherlands e-mail: [email protected]