Combinatorial array‐based enzymatic polyester synthesis

A combinatorial strategy for biocatalytic polymer synthesis is demonstrated. A library of polymers was synthesized in 96 deep‐well plates using AA‐BB polycondensations of acyl donors and acceptors. The library was based on four straight‐chain diesters as acyl donors (C 3 –C 10 ) with aliphatic/aromatic diols as well as more diverse structures including carbohydrates, nucleic acids, and a natural steroid diol used as acyl acceptors. The lipase from Candida antarctica was active in acetonitrile and was capable of catalyzing the polycondensation of the aforementioned monomers to polymers with M w 's reaching as high as 20,000 Da, including the preparation of novel sugar‐containing polyesters. The combinatorial approach to biocatalytic polymer synthesis described herein serves as a foundation for polymeric materials discovery by demonstrating that polymer arrays can be produced from structurally complex monomers. © 2001 John Wiley & Sons, Inc. Biotechnol Bioeng 76: 200–206, 2001.