Enzymatic polymerisation

Leslie Orgel and co-workers took up this problem and studied the non-enzymatic polymerisation of mononucleotides, i.e., the question as to whether single nucleic acid building blocks can undergo polycondensation on a corresponding complementary matrix. The substrates used were the 5 -phosphoimidazolides of adenosine (ImpA) and guanosine (ImpG), the matrices poly(U) and poly(C). 

Herdewijn established that enzymatic polymerisation of the pyranose nucleosidic triphosphates (81a-d) was possible, yielding structures that did not hybridise with DNA strands7 ... 

Scheme 6.15 Enzymatic polymerisation of globalide followed by thiol-ene postpolymerisation modification [45]...

In 2006, Heise s group reported a novel concept for the synthesis of chiral polyesters based on a lipase-catalysed DKR polymerisation of racemic diols." As shown in Scheme 4.25, a mixture of stereoisomers of a secondary diol was enzymatically polymerised with a difunctional acyl donor (dicarboxylic acid... 

For the synthesis of an optically active polyester from a racemic monomer, a new method of dynamic kinetic resolution was used. A mixture of stereoisomers of a secondary diol, a,a -dimethyl-l,4-benzenedimethanol, were enzymatically polymerised with dimethyl adipate (Scheme 12.6, [1]) [32]. 

Cyclic dicarbonates, cyclo /s(hexamethylene carbonate) and cyclo /s(diethylene glycol carbonate) were polymerised by lipase from C. antarctica and P. fluorescens [62]. CALB was used for the ROP of cyclo /s(decamethylene carbonate) (DMC2) giving a polymer with a MW of 5.4 x 10 and 99% yield, and an ultralow enzyme/substrate weight ratio of 1/200. Compared with six-membered trimethylene carbonate, a much lower reaction activity of large-sized DMC2 vvas observed, the opposite of the enzymatic polymerisation of lactones with different ring sizes [63]. 

The enzymatic polymerisation of phenol catalysed by EIRE was efficiently performed in phosphate buffer (pFI = 7.0) containing sodium dodecyl sulfate SDS, an environment-friendly system [171]. The obtained phenol polymer is partly soluble in common solvents, such as acetone, THE and DMF. IR analysis shows that the polymer is composed of phenylene and oxyphenylene units. The functionalisation of the phenol polymer was performed by reacting with epoxy chloropropane and triethylene-tetramine, the insoluble aminated phenol polymer was then obtained. The aminated phenol polymer was adopted as a carrier to prepare a novel supported palladium catalyst (PP-N-Pd) for the Heck reaction. 

Kobayashi and co-workers [218] reported that cellulose I and cellulose II can be selectively synthesised in vitro using the enzymatic polymerisation of the P-cellobiosyl fluoride monomer, and this selectivity could be controlled by changing the enzyme purity and polymerisation conditions. 

A cellulose-chitin hybrid polysaccharide with alternating P(1 4)-linked D-glucose (Glc) and N-acetyl-D-glucosamine (GlcNAc) was synthesised via two modes of enzymatic polymerisation [226]. First, a sugar oxazoline monomer of GlcP(1 4)... 

Finally, artificial polysaccharides produced via in vitro enzymatic synthesis [228] are new biomaterials with defined structures which either mimic natural polysaccharides or have nonnatural structures and functionalities. Polysaccharides are obtained by the enzymatic polymerisation of simple glycosyl donors via repetitive condensation. This approach not only provides a powerful methodology to produce polysaccharides with defined structures and morphologies as novel biomaterials, but also represents an available tool to analyse the mechanisms of polymerisation and packing in order to acquire high-order molecular assemblies. 

The extension of a polymer chain through enzymatic polymerisation results in a material response when the self-assembling properties of the polymer are changed as a result. Phosphorylase b has been used to extend the amylose part of a polymer amphiphUe by attaching further o-glucose-l-phosphate units to the end of the amylose chain (Morimoto et al., 2007) (Fig. 6.13). Terminal deoxynucleotidyltransferase (a DNA polymerase) was used to... 

Roy, S. and Ulijn, R. V. (2010). Exploiting biocatalysis in the synthesis of supra-molecular polymers. In Palmans, A. R. A. and Heise, A. (eds.) Enzymatic Polymerisation. Berlin Springer-Verlag Berlin. 

Duda A, Kowalski A, Penczek S, Uyama H, Kobayashi S (2002), Kinectics of the ring-opening polymerisation of 6-, 7-, 9-, 12-, 13-, 16-, and 17-membered lactones. Comparison of chemical and enzymatic polymerisations . Macromolecules, 35, 4266 270. 

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