title: Supramolecular Complexes Formed by the Self-assembly of Hydrophobic Bis(Zn(2+)-cyclen) Complexes, Copper, and Di- or Triimide Units for the Hydrolysis of Phosphate Mono- and Diesters in Two-Phase Solvent Systems (Cyclen=1,4,7,10-Tetraazacyclododecane).
abstract: We previously reported on supramolecular complexes 4 and 5, formed by the 4 : 4 : 4 or 2 : 2 : 2 assembly of a dimeric zinc(II) complex (Zn2L(1)) having 2,2'-bipyridyl linker, dianion of cyanuric acid (CA) or 5,5-diethylbarbituric acid (Bar), and copper(II) ion (Cu(2+)) in an aqueous solution. The supermolecule 4 possesses Cu2(μ-OH)2 centers and catalyzes hydrolysis of phosphate monoester dianion, mono(4-nitrophenyl)phosphate (MNP), at neutral pH. In this manuscript, we report on design and synthesis of hydrophobic supermolecules 9 and 10 by 4 : 4 : 4 and 2 : 2 : 2 self-assembly of hydrophobic Zn2L(2) and Zn2L(3) containing long alkyl chains, CA or Bar, and Cu(2+) and their phosphatase activity for the hydrolysis of MNP and bis(4-nitrophenyl)phosphate (BNP) in two-phase solvent systems. We assumed that the Cu2(μ-OH)2 active sites of 9 and 10 would be more stable in organic solvent than in aqueous solution and that product inhibition of the supermolecules might be avoided by the release of HPO4(2-) into the aqueous layer. The findings indicate that 9 and 10 exhibit phosphatase activity in the two-phase solvent system, although catalytic turnover was not observed. Furthermore, the hydrolysis of BNP catalyzed by the hydrophobic 2 : 2 : 2 supermolecules in the two-phase solvent system is described.
authors.affiliation: Faculty of Pharmaceutical Sciences, Tokyo University of Science.
authors.forename: Yosuke
authors.initials: Y
authors.lastname: Hisamatsu
authors.forename: Yuya
authors.initials: Y
authors.lastname: Miyazawa
authors.forename: Kakeru
authors.initials: K
authors.lastname: Yoneda
authors.forename: Miki
authors.initials: M
authors.lastname: Miyauchi
authors.forename: Mohd
authors.initials: M
authors.lastname: Zulkefeli
authors.forename: Shin
authors.initials: S
authors.lastname: Aoki
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry; D000080027:Cyclams; D004952:Esters / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006868:Hydrolysis; D057927:Hydrophobic and Hydrophilic Interactions; D007094:Imides / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D015032:Zinc / Q000737:chemistry
chemical_list: D000080027:Cyclams; D004952:Esters; D006571:Heterocyclic Compounds; D007094:Imides; D009942:Organometallic Compounds; D010710:Phosphates; D012997:Solvents; D003300:Copper; C038072:cyclen; D015032:Zinc