Journal
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
Volume 293, Issue 1-2, Pages 59-64Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.molcata.2008.07.010
Keywords
Cyclodextrin dimmer; Carboxylic ester; Hydrolysis; Zinc complex; Kinetics
Categories
Funding
- National Natural Science Foundation of China [20529101, 20671098, 20725103, 20770494]
- National Basic Research Program of China [2007CB815306]
- Natural Science Foundation of Guangdong Province [07117637]
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A new beta-cyclodextrin dimer, 2,2'-bipyridyl-4,4'-dimethyl-bridged-bis(6-monodeoxy-6-ammonio-beta-cyclodextrin) (BCD, Host) was synthesized and further assembled with a zinc complex containing a hydrophobic group as an inclusion complex, ZnL(BCD) (ZnL, L = 4-(4'-tertbutylbenzyl)diethylenetriamine, Guest). The complex was characterized by elemental analysis and NMR spectra and applied as a new supramolecular system of catalyzing carboxylic ester hydrolysis. In such host-guest system, the two deprotonation constants of the Zn-II-coordinated water molecules, 8.38 +/- 0.01 and 10.42 +/- 0.02 for pK(a1) and PKa2 respectively, were obtained by pH potentiometric titration at 298 +/- 0.1 K. The kinetics of p-nitrophenyl acetate (pNA) hydrolysis catalyzed by ZnL(BCD) was carried out at pH 7.54-10.56 and 298 +/- 0.1 K. The pH profile of observed hydrolysis rate constants catalyzed by ZnL(BCD) exhibits an exponential growth, indicating that the kinetic process is controlled by two acid-base equilibriums. Obtained kinetic results are in good agreement with thermodynamic data for hydroxyl active species in ZnL(BCD) system. Second-order rate constants of 0.15 and 2.64 M-1 s(-1) were calculated for mono- and di-hydroxyl active species in ZnL(BCD) system, respectively. Compared with an unassembled host or guest analogue, Zn(dien) (dien = diethylenetriamine), the supramolecular system exhibits much higher catalytic activity. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.
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