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Rhodium‐Complex‐Linked Hybrid Biocatalyst: Stereo‐Controlled Phenylacetylene Polymerization within an Engineered Protein Cavity
Author(s) -
Fukumoto Kazuki,
Onoda Akira,
Mizohata Eiichi,
Bocola Marco,
Inoue Tsuyoshi,
Schwaneberg Ulrich,
Hayashi Takashi
Publication year - 2014
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201301055
Subject(s) - phenylacetylene , chemistry , polymerization , biocatalysis , moiety , monomer , covalent bond , rhodium , maleimide , stereochemistry , polymer chemistry , polymer , organic chemistry , catalysis , reaction mechanism
The incorporation of a Rh complex with a maleimide moiety into the cavity of the nitrobindin β‐barrel scaffold by a covalent linkage at the 96‐position (Cys) provides a hybrid biocatalyst that promotes the polymerization of phenylacetylene. The appropriate structural optimization of the cavity by mutagenesis enhances the stereoselectivity of the polymer with a trans content of 82 % at 25 °C and pH 8.0. The X‐ray crystal structure of one of the hybrid biocatalysts at a resolution of 2.0 Å reveals that the Rh complex is located in the β‐barrel cavity without any perturbation to the total protein structure. Crystal structure analysis and molecular modeling support the fact that the stereoselectivity is enhanced by the effective control of monomer access to the Rh complex within the limited space of the protein cavity.