Copper(II)-Catalyzed Transamination between Pyruvate and Hydrophobic Pyridoxamine Embedded in Synthetic Bilayer Membranes

  • Yukito Murakami
    Department of Organic Synthesis, Faculty of Engineering, Kyushu University
  • Jun-ichi Kikuchi
    Department of Organic Synthesis, Faculty of Engineering, Kyushu University
  • Kazunari Akiyoshi
    Department of Organic Synthesis, Faculty of Engineering, Kyushu University

書誌事項

公開日
1985-04-01
権利情報
  • https://academic.oup.com/pages/standard-publication-reuse-rights
DOI
  • 10.1246/bcsj.58.1200
公開者
Oxford University Press (OUP)

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説明

<jats:title>Abstract</jats:title> <jats:p>The copper(II)-catalyzed transamination of 4-aminomethyl-5-[(dihexadecylamino)methyl]-2-methyl-3-pyridinol [(PM)2C16] with sodium pyruvate was investigated in an aqueous medium at pH 6.9, μ 0.10 (KCl), and 30.0±0.1 °C in the presence of single-walled bilayer vesicles of N,N-dihexadecyl-Nα-[6-(trimethylammonio)hexanoyl]-l-alaninamide bromide [N+C5Ala2C16] and N,N-dihexadecyl-Nα-[6-(trimethylammonio)hexanoyl]-l-histidinamide bromide [N+C5His2C16]. The binding mode of the pyridoxamine moiety in the vesicles was clarified by comparing the reaction behavior of the (PM)2C16–pyruvate–CuII system with that of the 4-aminomethyl-5-dodecylthiomethyl-2-methyl-3-pyridinol [(PM)C12]–pyruvate–CuII system. The pyridoxamine moiety of (PM)2C16 was more tightly anchored in the hydrogen-belt domain of the membranes than that of (PM)C12 as confirmed by fluorescence polarization spectroscopy. The difference in binding mode between (PM)2C16 and (PM)C12 is reflected on the copper(II)-coordination equilibria for the formation of the copper(II)–ketimine intermediates. The copper(II)-catalyzed transamination of (PM)2C16 with pyruvate in the N+C5His2C16 vesicle was most enhanced among related reaction systems treated here. The rate enhancement was attributed to the favorable formation of the reactive 2:1 ketimine–copper(II) chelate and the general-base catalysis by the coordination-free imidazolyl group of the lipid.</jats:p>

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