Macrocyclic polyamine Zinc complexes

Kimura, E., Shionoya, M., Hoshino, A., Ikeda, T., Yamada, Y., A model for catalytically active zinc(II) ion in liver alcohol-dehydrogenase - a novel hydride transfer-reaction catalyzed by zinc (II) -macrocyclic polyamine complexes. J. Am. Chem. Soc. 1992,114, 10134-10137. 

Koike T, Kimura E (1991) Roles of zinc(II) ion in phosphatases - a model study with zinc(II) macrocyclic polyamine complexes. J Am Chem Soc 113 8935-8941... 

The fundamental knowledge derived from the study of Zn macrocyclic polyamine complexes as zinc(II) enzyme models has been successfully developed to a new aspect of the molecular recognition of nucleic acid bases that contain an imide function in the heteroaromatic ring... 

A zinc(II) complex 22a with an alcohol-pendent polyamine has been synthesized (23). The alcoholic OH deprotonates with pifa of 8.6 (determined by pH-metric titration), yielding 22b. Reaction of 22 (2 mM) with a phosphotriester diethyl(4-nitrophenyl) phosphate (0.1 mM) in 10 mM TAPS buffer (pH 8.6) at 25°C seemed to promote phosphoryl-transfer reactions to 23, just like acyltransferred intermediates 10 and 16a in the reactions between Znn-macrocyclic complexes with an alcohol pendent and NA (see Scheme 4). The pH dependence of the first-order rate constants gave a sigmoidal curve with an inflection point around the pKa value of 8.6. The hydrolysis of the substrate phosphotriester to the phosphodiester product diethyl phosphate thus seemed to... 

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