title: The protein environment drives selectivity for sulfide oxidation by an artificial metalloenzyme.
abstract: MAGIC Mn-salen mETALLOZYME: The design of an original, artificial, inorganic, complex-protein adduct, has led to a better understanding of the synergistic effects of both partners. The exclusive formation of sulfoxides by the hybrid biocatalyst, as opposed to sulfone in the case of the free inorganic complex, highlights the modulating role of the inorganic-complex-binding site in the protein. Artificial metalloenzymes based on the incorporation of Mn-salen complexes into human serum albumin display high efficiency and selectivity for sulfoxide production during sulfide oxidation. The reactions carried out by the artificial metallozymes are comparable to those carried out by natural biocatalysis. We have found that the polarity of the protein environment is crucial for selectivity and that a synergy between both partners of the hybrid results in the novel activity.
authors.affiliation: Laboratoire de Chimie et Biologie des Métaux, Université Joseph Fourier, UMR 5249-CNRS, IRTSVCEA-Grenoble, Grenoble Cedex, France.
authors.forename: Pierre
authors.initials: P
authors.lastname: Rousselot-Pailley
authors.forename: Constance
authors.initials: C
authors.lastname: Bochot
authors.forename: Caroline
authors.initials: C
authors.lastname: Marchi-Delapierre
authors.forename: Adeline
authors.initials: A
authors.lastname: Jorge-Robin
authors.forename: Lydie
authors.initials: L
authors.lastname: Martin
authors.forename: Juan C
authors.initials: JC
authors.lastname: Fontecilla-Camps
authors.forename: Christine
authors.initials: C
authors.lastname: Cavazza
authors.forename: Stéphane
authors.initials: S
authors.lastname: Ménage
mesh_terms: D000975:Antioxidants / Q000737:chemistry; D002942:Circular Dichroism; D005029:Ethylenediamines / Q000737:chemistry; D006801:Humans; D008667:Metalloproteins / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D015202:Protein Engineering; D012709:Serum Albumin / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry*
chemical_list: D000975:Antioxidants; D005029:Ethylenediamines; D008667:Metalloproteins; D009942:Organometallic Compounds; D012709:Serum Albumin; D013440:Sulfides; C090577:N,N'-bis(salicylideneamino)ethane-manganese(II)