P-61 疎水性ビタミンB_<12>とヒト血清アルブミンによる人工酵素の構築とその反応特性(ポスター発表の部)

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We have been dealing with a hydrophobic vitamin B_<12>, heptapropyl cobyrinate perchlorate [Cob(II)7C_3ester] ClO_4, which has ester groups in place of the peripheral amide moieties of the naturally occurring vitamin B_<12>. In order to construct a good catalytic system, we prepared various artificial enzymes with vitamin B_<12> activities. One example is a vesicle-type artificial enzyme composed of peptide lipids and the hydrophobic vitamin B_<12>. Another one is a silica gel having vitamin B_<12> derivatives by the sol-gel method. In this work, we reported a new catalyst; human serum albumin (HSA) containing vitamin B_<12> derivatives. HSA is the most prominent protein in plasma, and serves as a transporter for hydrophobic molecules in vivo. We use HSA as an apoenzyme model for construction of an artificial B_<12> enzyme. The incorporation of hydrophobic vitamin B_<12> derivatives into HSA is primarily controlled by the hydrophobicity of the peripheral ester groups. Microenvironmental property around the hydrophobic vitamin B_<12> in HSA was examined by fluorescence and fluorescence polarization measurements. The hydrophobic vitamin B_<12> itself in HSA is in a microenvironment equivalent in medium polarity to dichloromethane. We added [Ru(II)(bpy)_3], as a photosensitizer, to a B_<12>-HSA artificial enzyme, and then carried out the degradation of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT), which is characterized by a pronounced insecticidal property and has been used worldwide for the last several decades despite its known hazardous effects on human health and wildlife, mediated by hydrophobic vitamin B_<12> under irradiation with visible light. DDT was decomposed to DDD and DDE, which are dechlorinated compounds. This result is very interesting from the viewpoint of green chemistry.
2008-09-01

P-61 疎水性ビタミンB_<12>とヒト血清アルブミンによる人工酵素の構築とその反応特性(ポスター発表の部)

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