title: Chemically engineered papain as artificial formate dehydrogenase for NAD(P)H regeneration.
abstract: Organometallic complexes of the general formula [(η(6)-arene)Ru(N⁁N)Cl](+) and [(η(5)-Cp*)Rh(N⁁N)Cl](+) where N⁁N is a 2,2'-dipyridylamine (DPA) derivative carrying a thiol-targeted maleimide group, 2,2'-bispyridyl (bpy), 1,10-phenanthroline (phen) or ethylenediamine (en) and arene is benzene, 2-chloro-N-[2-(phenyl)ethyl]acetamide or p-cymene were identified as catalysts for the stereoselective reduction of the enzyme cofactors NAD(P)(+) into NAD(P)H with formate as a hydride donor. A thorough comparison of their effectiveness towards NAD(+) (expressed as TOF) revealed that the Rh(III) complexes were much more potent catalysts than the Ru(II) complexes. Within the Ru(II) complex series, both the N⁁N and arene ligands forming the coordination sphere had a noticeable influence on the activity of the complexes. Covalent anchoring of the maleimide-functionalized Ru(II) and Rh(III) complexes to the cysteine endoproteinase papain yielded hybrid metalloproteins, some of them displaying formate dehydrogenase activity with potentially interesting kinetic parameters.
authors.affiliation: Chimie ParisTech, Laboratoire Charles Friedel, Paris, France.
authors.forename: Pierre
authors.initials: P
authors.lastname: Haquette
authors.forename: Barisa
authors.initials: B
authors.lastname: Talbi
authors.forename: Laure
authors.initials: L
authors.lastname: Barilleau
authors.forename: Nathalie
authors.initials: N
authors.lastname: Madern
authors.forename: Céline
authors.initials: C
authors.lastname: Fosse
authors.forename: Michèle
authors.initials: M
authors.lastname: Salmain
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000737:chemistry; D001554:Benzene / Q000737:chemistry; D000081007:Cymenes; D005029:Ethylenediamines / Q000737:chemistry; D005560:Formate Dehydrogenases / Q000737:chemistry*; D039821:Monoterpenes / Q000737:chemistry; D009249:NADP / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010206:Papain / Q000737:chemistry*; D010618:Phenanthrolines / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D000081007:Cymenes; D005029:Ethylenediamines; D039821:Monoterpenes; D009942:Organometallic Compounds; D010618:Phenanthrolines; C007210:4-cymene; D009249:NADP; D015082:2,2'-Dipyridyl; C031234:ethylenediamine; D012428:Ruthenium; D005560:Formate Dehydrogenases; D010206:Papain; D001554:Benzene; C025205:1,10-phenanthroline; C048062:2,2'-dipyridylamine