Abstract
Lipase from Candida rugosa was loaded into an amphiphilic polymer co-network (APCN) composed of the chiral poly[(R)-N-(1-hydroxybutan-2-yl) acrylamide] [P-(R)-HBA] and P-(S)-HBA, respectively, linked by poly(dimethylsiloxane). The nanophase-separated amphiphilic morphology affords a 38,000-fold activation of the enzyme in the esterification of 1-phenylethanol with vinyl acetate. Further, the enantioselectivity of the entrapped lipase was influenced by the configuration of the chiral, hydrophilic polymer matrix. While the APCN with the (S)-configuration of the APCN affords 5.4 faster conversion of the (R)-phenylethanol compared to the respective (S)-enantiomer, the (R)-APCN allows an only a 2.8 faster conversion of the (R)-enantiomer of the alcohol. Permeation-experiments reveal that the enantioselectivity of the reaction is at least partially caused by specific interactions between the substrates and the APCN.
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References
Adlercreutz P (2013) Immobilisation and application of lipases in organic media. Chem Soc Rev 42(15):6406–6436
Broos J, Kakodinskaya IK, Engbersen JFJ, Verboom W, Reinhoudt DN (1995) Large activation of serine proteases by pretreatment with crown ethers. J Chem Soc Chem Commun 2:255–256
Bruns N, Tiller JC (2005) Amphiphilic network as nanoreactor for enzymes in organic solvents. Nano Lett 5:45–48
Bruns N, Tiller JC (2006) Nanophasic amphiphilic co-networks with a fluorophilic phase. Macromolecules 39:4386–4394
Bruns N, Bannwarth W, Tiller JC (2008) Amphiphilic co-networks as activating carriers for the enhancement of enzymatic activity in supercritical CO2. Biotechnol Bioeng 101(1):19–26
Carrea G, Riva S (2000) Properties and synthetic applications of enzymes in organic solvents. Angew Chem Int Ed Engl 39:2226–2254
Dech S, Cramer T, Ladisch R, Bruns N, Tiller JC (2011) Solid–solid interface adsorption of proteins and enzymes in nanophase-separated amphiphilic co-networks. Biomacromolecules 12:1594–1601
Erdodi G, Kennedy JP (2006) Amphiphilic co-networks: definition, synthesis, applications. Prog Polym Sci 31:1–18
Fitzpatrick PA, Klibanov AM (1991) How can the solvent affect enzyme enantioselectivity. J Am Chem Soc 113:3166–3171
Godoy CA, Romero O, delas Rivas B, Mateo C, Fernandez-Lorente G, Guisan JM, Palomo JM (2013) Changes on enantioselectivity of a genetically modified thermophilic lipase by site-directed oriented immobilization. J Mol Catal B 87:121–127
Khmelnitsky YL, Welch SH, Clark DS, Dordick JS (1994) Salts dramatically enhance activity of enzymes suspended in organic solvents. J Am Chem Soc 116:2647–2648
Mallin H, Menyes U, Vorhaben T, Hoehne M, Bornscheuer UT (2013) Immobilization of two (R)-amine transaminases on an optimized chitosan support for the enzymatic synthesis of optically pure amines. ChemCatChem 5:588–593
Natalia D, Greiner L, Leitner W, Ansorge-Schumacher MB (2012) Stability, activity, and selectivity of benzaldehyde lyase in supercritical fluids. J Supercrit Fluids 62:173–177
Paradkar VM, Dordick JS (1994) Aqueous-like activity of alpha-chymotrypsin dissolved in nearly anhydrous organic solvents. J Am Chem Soc 116:5009–5010
Reetz MT (1997) Entrapment of biocatalysts in hydrophobic sol–gel materials for use in organic chemistry. Adv Mater 9(12):943–954
Reetz MT, Wilensek S, Zha D, Jaeger K-E (2001) Directed evolution of an enantioselective enzyme through combinatorial multiple-cassette mutagenesis. Angew Chem Int Ed Engl 40:3589–3591
Schoenfeld I, Dech S, Ryabenky B, Daniel B, Glowacki B, Ladisch R, Tiller JC (2013) Investigations on diffusion limitations of biocatalyzed reactions in amphiphilic polymer co-networks in organic solvents. Biotechnol Bioeng 110:2333–2342
Tobis J, Thomann Y, Tiller JC (2010) Synthesis and characterization of chiral and thermo responsive amphiphilic co-networks. Polymer 51:35–45
Tobis J, Boch L, Thomann Y, Tiller JC (2011) Amphiphilic polymer co-networks as chiral separation membranes. J Membr Sci 372:219–227
Wang P, Sergeeva MV, Lim L, Dordick JS (1997) Biocatalytic plastics as active and stable materials for biotransformations. Nat Biotechnol 15(8):789–793
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Tobis, J., Tiller, J.C. Impact of the configuration of a chiral, activating carrier on the enantioselectivity of entrapped lipase from Candida rugosa in cyclohexane. Biotechnol Lett 36, 1661–1667 (2014). https://doi.org/10.1007/s10529-014-1519-0
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DOI: https://doi.org/10.1007/s10529-014-1519-0