Poly lipase-catalyzed synthesis

Hayes, D.G. Lipase-catalyzed synthesis of poly-hydric alcohol-poly(ricinoleic acid) ester star polymers. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2005, 46 (1), 276-277. 

Lipase-catalyzed synthesis of poly(l,4-butyl sebacate) from reactions of 1,4-butanediol and sebacic acid or activated derivatives of sebacic acid were studied by Linko et al. [51]. Reactions between 1,4-butanediol with sebacic acid,... 

The phase separation of reactants hindered attempts to carry out lipase-catalyzed synthesis of poly(butylene succinate) (PBS) from succinic acid and 1,4-butanediol via dehydration. Therefore, in order to obtain a monophasic reaction mixture, dimethyl succinate was used in place of succinic acid. [49] The reaction mixture remained monophasic during the reaction course, and after 21 h at 95 °C PBS with M of 38000 was obtained. 

Scheme 4.27 Pseudomonas fluorescens lipase-catalyzed synthesis of poly (MBC-co-TMC).

J. (1995) Lipase-catalyzed synthesis of poly(1,4-butyl sebacate) from sebacic acid or its derivatives with 1,4-butanediol./. Biotechnol., 40 (2), 133-138. 

Jiang, Y., Liu, C., and Gross, R.A. (2008) Lipase-catalyzed synthesis of aliphatic poly(carbonate-co-esters). Macromolecules, 41 (13), 4671-4680. 

Scheme 11.1 Lipase-catalyzed synthesis of poly(L-lactide) (10).

Poojari, Y. Clarson, S. J., Lipase Catalyzed Synthesis and Thermal Properties of Poly(dimethylsiloxane)-Poly(ethylene glycol) Amphiphilic Block Copolymers. J. Inorg. Organomet. Polym. 2010,20, 46-52. 

General procedure for the lipase-catalyzed synthesis of poly(l,8-octanyladipate-co-sorbityladipate) terpolyesters ... 

The fatty esters of polyethers are known to be good surfactants, and many commercial products are available in the market place. Most people use chemical methods to achieve the required synthesis. Enzymatic methods can also be used however, the reaction needs to be optimized. An example is the lipase-catalyzed synthesis of fatty acid diester of poly(ethylene glycol) EG). 

Lipase-Catalyzed Synthesis of Poly(Hydroxy Acid) Esters... 

Kelly, A.R., Hayes, D.G., 2006. Lipase-catalyzed synthesis of polyhydric alcohol-poly(ricinoleic add) esta- star polymars. J. Appl. Polym. Sci. 101, 1646-1656. 

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]. 

Feng Y, Klee D, Keul H, Hdcker H (2000) Lipase-catalyzed ring-opening polymerization of morpholine-2,5-dione derivatives a novel route to the synthesis of poly(ester amide)s. Macromol Chem Phys 201 2670-2675... 

Ester synthesis of fatty acid ethyl ester. The lipase-catalyzed esterification of fatty acid and alcohol is well-known. It was also favorable for the esterification of poly unsaturated fatty acids under mild conditions with the enzyme. However, the activity of native lipase is lower in polar organic solvents, i.e. ethanol and methanol. The synthesis of Ae fatty acid ethyl ester was carried out in ethanol using the palmitic acid-modified lipase. As shown in Figure 7, the reactivity of the modified lipase in this system was much higher than that of the unmoditied lipase. 

Azim, H., Dekhterman, A., Jiang, Z., and Gross, R.A. (2006) Candida antarctica lipase B-catalyzed synthesis of poly(butylene succinate) shorter chain building blocks also work. Biomacromolecules, 7 (11), 3093-3097. 

In an elegant recent work, Loos et al. [51, 52] reported the synthesis of polydialanine) via lipase-catalyzed ring-opening of 2-azetidinone (Scheme 5.4) (see Chapter 14 for details on the polymerization mechanism). After removal of cyclic side products and low-molecular-weight species, pure linear poly(P-alanine) was obtained. The average DP of the polymer obtained was limited to 8 because of the solubility of the polymer in the reaction medium. Control experiments with P-alanine as substrate confirmed that the ring structure of the 2-azetidinone was necessary to obtain the polymer. 

The synthesis of chiral poly(depsipeptides), polymers with alternating amide and ester bonds, by lipase-catalyzed ring opening of 3-isopropyl morpholino-2,5-dione (19) was shown by Hocker and coworkers (Scheme 11.5) [26], Various lipases were tested for the bulk polymerization of these heterocyclic monomers at temperatures of 100 °C or above. PPL and lipase type III from a pseudomonas species were shown to be effective catalysts. The isolated polymers showed Mn values of 3.5-17.5 kgmol-1. The influence of reaction temperature, the amount of enzyme and the presence of water in the reaction medium were shown to be important factors on the high molecular weight fraction and were investigated in detail [26b]. Comparison of optical rotation values for polymers prepared by... 

Candida antarctica Lipase B Catalyzed Synthesis of Poly(butylene succinate) Shorter Chain Building Blocks Also Work... 

Single-step synthesis of polyester macromonomers was achieved by lipase-catalyzed polymerization of lactones in the presence of vinyl esters acting as terminator ( terminator method ) (187,188). A methacryl-type poly(DDL) macromonomer was obtained using vinyl methacrylate (12.5 or 15 mol% based on DDL) and lipase PF as terminator and catalyst, respectively. By the addition of divinyl sebacate, the telechelic polyester having a carboxylic acid group at both ends was synthesized. 

Nakai H, Kitaoka M, Svensson B, Ohtsubo K (2013) Recent development of phosphorylases possessing large potential for oligosaccharide synthesis. Curr Opin Chem Biol 17 301-309 Nomura S, Kyotoku T, Shimomura N, Kaneko Y, Kadokawa J (2011) Preparation of inclusion complexes composed of amylose and biodegradable poly(glycolic acid-co-e-caprolactone) by vine-twining polymerization and their lipase-catalyzed hydrolysis behavior. Polym J 43 971-977... 

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