Biocatalytic plastics

Wang, P., Sergeeva, M.V., Lim, L. and Dordick, J.S. (1997) Biocatalytic plastics as active and stable materials for biotransformations. Nature Biotechnology, 15, 789-793. 

More complicated immobilization methods have been described, including covalent attachment to a support, entrapment inside particles (such as silica made by a sol-gel process), and covalent incorporation into polymer particles ( biocatalytic plastics ). However, it is not clear that any of these methods is superior to simple adsorption, particularly for use in low-water media, where enzyme desorption is not an issue. 

Parallel approaches have been described for the preparation of polyacrylate-protease conjugates [396-400]. Acryloylation of subtilisin and a-chymotrypsin, followed by mixed polymerization with methyl methacrylate, vinyl acetate, styrene, or ethylvinyl ether, provides insoluble, doped polymethyl methacrylate, polyvinyl acetate, polystyrene, and polyethyl vinyl ether polymers [396]. These biocatalytic plastics perform especially well in hydrophilic and hydrophobic solvents, and have been used for peptide synthesis and the regioselective acylation of sugars and nucleosides. Similarly, modification of subtilisin and thermolysin with PEG monomethacrylate, then copolymerization with methyl methacrylate and trimethylolpropane trimethacrylate furnishes protease-polymethyl methacrylate plastics, which show good activities and stabilities in aqueous, mixed, and low-water and anhydrous organic media [397-400]. The protein-acrylate composites are unique in that they enable catalytic densities as high as 50% w/w. 

The ADMET polymerization of sugar-based monomers is much less explored than the ROMP approach, and only a few examples have been reported to date. Bui and Hudlicky prepared a,oo-dienes derived from a biocatalytically synthesized diene diol, from which chiral polymers (up to 20 kDa) with D-c/uro-inositol units were prepared via ADMET in the presence of 1 mol% of C4 [169]. Furthermore, several ot,co-dienes containing D-mannitol, D-ribose, D-isomannide, and D-isosorbide have been synthesized by Enholm and Mondal [170]. Also in this study, C4 was used to catalyze the ADMET polymerizations at 1 mol% catalyst loading. As pointed out by the authors, the viscosity increased as the reactions progressed and vacuum had to be applied to efficiently remove the released ethylene. Unfortunately, the polymers obtained were not further analyzed. As already mentioned above, Fokou and Meier have also reported the ADMET polymerization of a fatty acid-/D-isosorbide-based a,co-diene [126]. Furthermore, Krausz et al. have synthesized plastic films with good mechanical properties by cross-linking fatty esters of cellulose in the presence of C3 [171-173]. 

Renewable raw materials can contribute to the sustainability of chemical products in two ways (i) by developing greener, biomass-derived products which replace existing oil-based products, e.g. a biodegradable plastic, and (ii) greener processes for the manufacture of existing chemicals from biomass instead of from fossil feedstocks. These conversion processes should, of course, be catalytic in order to maximize atom efficiencies and minimize waste (E factors) but they could be chemo- or biocatalytic, e.g. fermentation [3-5]. Even the chemocatalysts themselves can be derived from biomass, e.g. expanded com starches modified with surface S03H or amine moieties can be used as recyclable solid acid or base catalysts, respectively [6]. 

Skjot, M., De Maria, L., Chatterjee, R., Svendsen, A., Patkar, S.A., 0stergaard, P.R.,and Brask,). (2009) Understanding the plasticity of the alpha/beta-hydrolase fold lid swapping on the Candida antarctica lipase B results in chimeras with interesting biocatalytic properties. ChemBioChem., 10,520-527. 

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