title: Selective hydrolysis of phosphate monoester by a supramolecular phosphatase formed by the self-assembly of a bis(Zn(2+)-cyclen) complex, cyanuric acid, and copper in an aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane).
abstract: In Nature, organized nanoscale structures such as proteins and enzymes are formed in aqueous media via intermolecular interactions between multicomponents. Supramolecular and self-assembling strategies provide versatile methods for the construction of artificial chemical architectures for controlling reaction rates and the specificities of chemical reactions, but most are designed in hydrophobic environments. The preparation of artificial catalysts that have potential in aqueous media mimicking natural enzymes such as hydrolases remains a great challenge in the fields of supramolecular chemistry. Herein, we describe that a dimeric Zn(2+) complex having a 2,2'-bipyridyl linker, cyanuric acid, and a Cu(2+) ion automatically assembles in an aqueous solution to form a 4:4:4 complex, which is stabilized by metal-ligand coordination bonds, π-π-stacking interactions, and hydrogen bonding and contains μ-Cu(2)(OH)(2) cores analogous to the catalytic centers of phosphatase, a dinuclear metalloenzyme. The 4:4:4 complex selectively accelerates the hydrolysis of a phosphate monoester, mono(4-nitrophenyl)phosphate, at neutral pH.
authors.affiliation: Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
authors.forename: Mohd
authors.initials: M
authors.lastname: Zulkefeli
authors.forename: Asami
authors.initials: A
authors.lastname: Suzuki
authors.forename: Motoo
authors.initials: M
authors.lastname: Shiro
authors.forename: Yosuke
authors.initials: Y
authors.lastname: Hisamatsu
authors.forename: Eiichi
authors.initials: E
authors.lastname: Kimura
authors.forename: Shin
authors.initials: S
authors.lastname: Aoki
mesh_terms: D000818:Animals; D040761:Biomimetic Materials / Q000737:chemistry; D020134:Catalytic Domain; D003300:Copper / Q000737:chemistry*; D017839:Crotalus; D018360:Crystallography, X-Ray; D000080027:Cyclams; D004926:Escherichia coli / Q000201:enzymology; D004952:Esters; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D008958:Models, Molecular; D009596:Nitrophenols / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D009943:Organophosphorus Compounds / Q000737:chemistry; D010710:Phosphates / Q000737:chemistry*; D010727:Phosphoric Diester Hydrolases / Q000378:metabolism; D010744:Phosphoric Monoester Hydrolases / Q000737:chemistry / Q000378:metabolism*; D012996:Solutions; D013379:Substrate Specificity; D014227:Triazines / Q000737:chemistry*; D014867:Water / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D000080027:Cyclams; D004952:Esters; D006571:Heterocyclic Compounds; D009596:Nitrophenols; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D010710:Phosphates; D012996:Solutions; D014227:Triazines; D014867:Water; C008644:nitrophenylphosphate; D003300:Copper; C038072:cyclen; D010744:Phosphoric Monoester Hydrolases; D010727:Phosphoric Diester Hydrolases; C004632:cyanuric acid; D015032:Zinc