Polyesters enzymic synthesis

D. R. Patil, D. G. Rethwisch, and J. S. Dordick, Enzymic synthesis of a sucrose-containing linear polyester in nearly anhydrous organic media, Biotechnol. Bioeng., 37 (1991) 639-646. 

Enzymes are generally classified into six groups. Table 1 shows typical polymers produced with catalysis by respective enzymes. The target macromolecules for the enzymatic polymerization have been polysaccharides, poly(amino acid)s, polyesters, polycarbonates, phenolic polymers, poly(aniline)s, vinyl polymers, etc. In the standpoint of potential industrial applications, this chapter deals with recent topics on enzymatic synthesis of polyesters and phenolic polymers by using enzymes as catalyst. 

In vitro synthesis of polyesters using isolated enzymes as catalyst via non-biosynthetic pathways is reviewed. In most cases, lipase was used as catalyst and various monomer combinations, typically oxyacids or their esters, dicarboxylic acids or their derivatives/glycols, and lactones, afforded the polyesters. The enzymatic polymerization often proceeded under mild reaction conditions in comparison with chemical processes. By utilizing characteristic properties of lipases, regio- and enantioselective polymerizations proceeded to give functional polymers, most of which are difficult to synthesize by conventional methodologies. 

The conventional synthesis of aliphatic polyesters based on adipic acid and a range of diols, such as 1,4-butanediol or 1,6-hexanediol, involves a high-temperature esterification reaction typically at 240-260 °C and an organometallic catalyst such as stannous octano-ate. The use of enzyme catalysis results in a much lower reaction temperature, but also the possibility of removing the esterification catalyst, giving the polyester significantly improved hydrolysis resistance. 

Binns, F., Harffey, P., Roberts, S.M. and Taylor, A., Studies leading to the large scale synthesis of polyesters using enzymes. J. Chem. Soc. Perkin Trans. 1999, 2671. 

This review aims at reporting on the synthesis of aliphatic polyesters by ROP of lactones. It is worth noting that lactones include cyclic mono- and diesters. Typical cyclic diesters are lactide and glycolide, whose polymerizations provide aliphatic polyesters widely used in the frame of biomedical applications. Nevertheless, this review will focus on the polymerization of cyclic monoesters. It will be shown that the ROP of lactones can take place by various mechanisms. The polymerization can be initiated by anions, organometallic species, cations, and nucleophiles. It can also be catalyzed by Bronsted acids, Lewis acids, enzymes, organic nucleophiles, and bases. The number of processes reported for the ROP of lactones is so huge that it is almost impossible to describe aU of them. In this review, we will focus on the more... 

Knani D, Gutman AL, Kohn DH (1993) Enzymatic polyesterification in organic media. Enzyme-catalyzed synthesis of linear polyesters. I. Condensation polymerization of linear hydroxyester. II. Ring-opening polymerization of e-caprolactone. J Polym Sci A Polym Chem 31 1221-1232... 

Varma IK, Albertsson A-C, Rajkhowa R, Srivistava RK (2005) Enzyme catalyzed synthesis of polyesters. Prog Polym Sci 30 949-981... 

Lipases are enzymes that catalyze the in vivo hydrolysis of lipids such as triacylglycerols. Lipases are not used in biological systems for ester synthesis, presumably because the large amounts of water present preclude ester formation due to the law of mass action which favors hydrolysis. A different pathway (using the coenzyme A thioester of a carboxylic acid and the enzyme synthase [Blei and Odian, 2000]) is present in biological systems for ester formation. However, lipases do catalyze the in vitro esterification reaction and have been used to synthesize polyesters. The reaction between alcohols and carboxylic acids occurs in organic solvents where the absence of water favors esterification. However, water is a by-product and must be removed efficiently to maximize conversions and molecular weights. 

Abstract Transferases are enzymes that catalyze reactions in which a group is transferred from one compound to another. This makes these enzymes ideal catalysts for polymerization reactions. In nature, transferases are responsible for the synthesis of many important natural macromolecules. In synthetic polymer chemistry, various transferases are used to synthesize polymers in vitro. This chapter reviews some of these approaches, such as the enzymatic polymerization of polyesters, polysaccharides, and polyisoprene. 

Production of polymers contributes to pollution during synthesis and after use. A polymer produced by microorganisms is already a commercial product (Biopol). Unfortunately, however, cellular synthesis remains limited by the cost of downstream processing and the fact that the synthesis is aqueous-based, and it is impossible to perform the synthesis in the absence of a solvent. Recent research describes an enzyme-catalyzed polymer synthesis in which there is no solvent. This bulk polymerization mirrors conventional synthesis but eliminates the needs for extremes of temperature and corrosive acid catalysts. This represents the first rapid and efficient synthesis of polyesters from bulk polymerization under ambient conditions with very low concentrations of a biocatalyst (Chaudhary et al., 1997). 

Lipase Transesterification and direct esterification (inch polyester synthesis) Ring-opening polymerization of 8-caprolactone Hydrolysis alcoholysis acetylation Higher stability of enzyme greater activity catalyst recyclable sometimes higher enantio- and regio-selectivity compared with VOCs... 

Gross, R.A. Kalra, B. Kumar, A. Polyester and polycarbonate synthesis by in vitro enzyme catalysis. Appl. Microbiol. Biotechnol. 2001, 55 (6), 655-660. 

Chaudhary, A. K., Beckman, E. J., and Russell, A. J., Rational control of polymer molecular weight and dispersity during enzyme-catalyzed polyester synthesis in supercritical fluids, J. Am. Chem. Soc., 117, 3728-3733, 1995. 

Okumara et al. [10] were the first to attempt the enzyme-catalyzed synthesis of oligoesters from a reaction between dicarboxylic acids and diols. Gutman et al. [11] reported the first study on polyester synthesis by enzyme-catalyzed polymerization of A-B type monomers. Two independent groups in 1993 [12, 13] were first to report enzyme-catalyzed ring-opening polymerization (ROP). Their studies focused on 7- and 6-membered unsubstituted cyclic esters, e-caprolactone (e-CL) and 8-valerolactone (8-VL), respectively. 

Among enzymes, lipases proved to be the most efficient for the in vitro polyester synthesis. Lipases or triacylglycerol acylhydrolases are water-soluble enzymes that catalyze the hydrolysis of ester bonds in water-insoluble, lipid substrates, and therefore comprise a subclass of the esterases. 

Scheme 4.1 Two basic modes of enzyme-catalyzed polyester synthesis.

Scheme 4.10 Enzyme-catalyzed synthesis of epoxy-containing polyester.

Matsumura, S. (2002) Enzyme-catalyzed synthesis and chemical recycling of polyesters. Macromol. Biosci., 2 (3), 105-126. 

J. (1995) Lipase-catalyzed linear aliphatic polyester synthesis in organic solvent. Enzyme. Microb. Technol., 17 (6), 506-511. 

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