title: Incorporation of manganese complexes into xylanase: new artificial metalloenzymes for enantioselective epoxidation.
abstract: Here we report the best artificial metalloenzyme to date for the selective oxidation of aromatic alkenes; it was obtained by noncovalent insertion of Mn(III)-meso-tetrakis(p-carboxyphenyl)porphyrin [Mn(TpCPP), 1-Mn] into a host protein, xylanase 10A from Streptomyces lividans (Xln10A). Two metallic complexes-N,N'-ethylene bis(2-hydroxybenzylimine)-5,5'-dicarboxylic acid Mn(III) [(Mn-salen), 2-Mn] and 1-Mn-were associated with Xln10A, and the two hybrid biocatalysts were characterised by UV-visible spectroscopy, circular dichroism and molecular modelling. Only the artificial metalloenzyme based on 1-Mn and Xln10A was studied for its catalytic properties in the oxidation of various substituted styrene derivatives by KHSO(5): after optimisation, the 1-Mn-Xln10A artificial metalloenzyme was able to catalyse the oxidation of para-methoxystyrene by KHSO(5) with a 16 % yield and the best enantioselectivity (80 % in favour of the R isomer) ever reported for an artificial metalloenzyme.
authors.affiliation: Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Laboratoire de Chimie Bioorganique et Bioinorganique, Bâtiment 420, Université Paris XI, 91405 Orsay Cedex, France.
authors.forename: Mathieu
authors.initials: M
authors.lastname: Allard
authors.forename: Claude
authors.initials: C
authors.lastname: Dupont
authors.forename: Victor
authors.initials: V
authors.lastname: Muñoz Robles
authors.forename: Nicolas
authors.initials: N
authors.lastname: Doucet
authors.forename: Agustí
authors.initials: A
authors.lastname: Lledós
authors.forename: Jean-Didier
authors.initials: JD
authors.lastname: Maréchal
authors.forename: Agathe
authors.initials: A
authors.lastname: Urvoas
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Mahy
authors.forename: Rémy
authors.initials: R
authors.lastname: Ricoux
mesh_terms: D002384:Catalysis; D002942:Circular Dichroism; D043364:Endo-1,4-beta Xylanases / Q000737:chemistry* / Q000378:metabolism; D004852:Epoxy Compounds / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry* / Q000378:metabolism; D008667:Metalloproteins / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013056:Spectrophotometry, Ultraviolet; D013237:Stereoisomerism; D020058:Styrene / Q000737:chemistry
chemical_list: D004852:Epoxy Compounds; D008667:Metalloproteins; D008345:Manganese; D020058:Styrene; D043364:Endo-1,4-beta Xylanases