| Project/Area Number |
16550137
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Environmental chemistry
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| Research Institution | Yokohama City University |
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Principal Investigator |
MOCHIZUKI Katsura Yokohama City University, Internatonal Graduate School of Art and Science, Professor, 国際総合科学研究科, 教授 (60150562)
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| Project Period (FY) |
2004 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥2,300,000 (Direct Cost: ¥2,300,000)
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| Keywords | Bisphenol A / Macocyclic ligands / Copper complexes / Oxidation |
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| Research Abstract |
New macrocyclic ligands and their metal complexes were synthesized and used for the studies on the activation of molecular oxygen and the oxidation of phenols in acetonitrile under oxygen atmosphere. We have revealed that copper(I) complexes with some macrocyclic ligands bearing benzyl substituents can activate molecular oxygen, which induces the orth-hydroxylation of phenols (ex., methylbenzoate) to afford corresponding catechols and/or quinones. The oxidation reaction of bisphenol A (endocrine disruptor) was also investigated. The mono-quinone compound with less estrogenic activity than bisphenol A was identified as the oxidation product. These results suggest that our oxidation method using copper complex has a possibility to become one of mild and effective methods for degradation of endocrine disruptor phenols.
The formation of oxygen coordinated copper complexes with tetraaza macrocyclic ligands was elucidated spectrophotometrically. VIS-absorption spectra of a butyronitrile solution containing the macrocyclic copper(I) complex and oxygen measured at 183 K clearly showed the formation of the oxygen-copper complex with the macrocyclic ligand. The oxygen-copper complex observed at low temperature is considered to be intermediate species during the phenol-oxidation reactions.
In order to build up a model for the trinuclear active site of Laccase, trinucleating bismacrocyclic ligands have been synthesized. The bismacrocyclic ligands, where two macrocycles are likned by a bipyridine bridge, actually form trinuclear metal complexes as the structural model of the active site.
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