title: Design of a dinuclear nickel(II) bioinspired hydrolase to bind covalently to silica surfaces: synthesis, magnetism, and reactivity studies.
abstract: Presented herein is the design of a dinuclear Ni(II) synthetic hydrolase [Ni(2)(HBPPAMFF)(μ-OAc)(2)(H(2)O)]BPh(4) (1) (H(2)BPPAMFF = 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4-methyl-6-formylphenol) to be covalently attached to silica surfaces, while maintaining its catalytic activity. An aldehyde-containing ligand (H(2)BPPAMFF) provides a reactive functional group that can serve as a cross-linking group to bind the complex to an organoalkoxysilane and later to the silica surfaces or directly to amino-modified surfaces. The dinuclear Ni(II) complex covalently attached to the silica surfaces was fully characterized by different techniques. The catalytic turnover number (k(cat)) of the immobilized Ni(II)Ni(II) catalyst in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate is comparable to the homogeneous reaction; however, the catalyst interaction with the support enhanced the substrate to complex association constant, and consequently, the catalytic efficiency (E = k(cat)/K(M)) and the supported catalyst can be reused for subsequent diester hydrolysis reactions.
authors.affiliation: Departamento de Química, Laboratório de Química Bioinorgânica e Cristalografia (LABINC), Universidade Federal de Santa Catarina, SC, 88040-900 Florianópolis, Brazil.
authors.forename: Clovis
authors.initials: C
authors.lastname: Piovezan
authors.forename: Jaqueline M R
authors.initials: JM
authors.lastname: Silva
authors.forename: Ademir
authors.initials: A
authors.lastname: Neves
authors.forename: Adailton J
authors.initials: AJ
authors.lastname: Bortoluzzi
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Haase
authors.forename: Zbigniew
authors.initials: Z
authors.lastname: Tomkowicz
authors.forename: Eduardo E
authors.initials: EE
authors.lastname: Castellano
authors.forename: Tessa C S
authors.initials: TC
authors.lastname: Hough
authors.forename: Liane M
authors.initials: LM
authors.lastname: Rossi
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry* / Q000378:metabolism; D018360:Crystallography, X-Ray; D006867:Hydrolases / Q000737:chemistry* / Q000378:metabolism; D006868:Hydrolysis; D008024:Ligands; D008958:Models, Molecular; D054118:Nanospheres / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry* / Q000378:metabolism; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D012822:Silicon Dioxide; D009532:Nickel; D006867:Hydrolases