Abstract：
:To construct the model of metallohydrolase, two inclusion complexes [MLCl2(β-CD)] (1, M=Zn(II); 2, M=Cu(II); L=N,N'-bis(2-pyridylmethyl)amantadine; β-CD=β-cyclodextrin) were synthesized by mixing β-CDs with the pre-synthesized complexes G1, [ZnLCl2] and G2, [CuLCl2]. Structures of G1, G2, 1 and 2 were characterized by X-ray crystallography, respectively. In solution, two chloride anions of G1 and G2 underwent ligand exchange with solvent molecules according to ESI-MS analysis. The chemical equilibrium constants were determined by potentiometric pH titration. The kinetics of bis(4-nitrophenyl) phosphate (BNPP) hydrolysis catalyzed by G1, G2, 1 and 2 were examined at pHs ranging from 7.50 to 10.50 at 308±0.1K. The pH profile of rate constant of BNPP hydrolysis catalyzed by 1 exhibited an exponential increase with the second-order rate constant of 2.68×10-3M-1s-1 assigned to the di-hydroxo species, which was approximately an order of magnitude higher than those of reported mono-Zn(II)-hydroxo species. The high reactivity was presumably hydroxyl-rich microenvironment provided by β-CDs, which might effect in stabilizing either the labile zinc-hydroxo species or the catalytic transition state.
journal_name
J Inorg Biochemjournal_title
Journal of inorganic biochemistryauthors
Zhou YH,Chen LQ,Tao J,Shen JL,Gong DY,Yun RR,Cheng Ydoi
10.1016/j.jinorgbio.2016.07.011subject
Has Abstractpub_date
2016-10-01 00:00:00pages
176-184eissn
0162-0134issn
1873-3344pii
S0162-0134(16)30212-4journal_volume
163pub_type
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