Macrocyclic enzyme model system. Kinetic activity of (20)paracyclophane bearing 1,4-dihydronicotinamide and 2-pyridinecarboxylic acid moieties as effected by zinc ion.
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概要
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As regards the effect of zinc(II) ion on the reduction of hexachloroacetone, the kinetic activity of a [20]paracyclophane (PCP) bearing 1,4-dihydronicotinamide (HNA) and 2-pyridinecarboxylic acid (Py) moieties, HNA–PCP–Py, has been investigated as an alcohol dehydrogenase model in reference to that of PCP–HNA in the light of their metal-coordination behavior. The reduction ability of PCP–HNA was significantly lowered as it underwent complex formation with zinc. On the other hand, HNA–PCP–Py showed an apparent rate maximum in a relatively lower concentration range of ZnCl<SUB>2</SUB>. The kinetic behavior was analyzed on the basis of the formation of two kinds of zinc complexes of HNA–PCP–Py: the 1:1 complex (<U>Remark: Graphics omitted.</U>), in which both Py and HNA moieties are simultaneously coordinated to the same zinc ion, showed a decreased reactivity relative to metal-free HNA–PCP–Py; while the 2:1 complex (HNA–PCP–Py–Zn<SUP>II</SUP>–Py–PCP–HNA), in which HNA is free from metal-coordination, exercised a much enhanced activity, 7 times as reactive as metal-free HNA–PCP–Py. A plausible reaction mechanism for the enhanced reactivity has been discussed.
著者
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Murakami Yukito
Department Of Chemical Science And Technology Faculty Of Engineering Kyushu University
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KIKUCHI Jun-ichi
Department of Applied Chemistry, Faculty of Science and Engineering, Saga University
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Aoyama Yasuhiro
Department Of Chemistry Nagaoka University Of Technology
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