1996 Fiscal Year Final Research Report Summary
Dynamics of Amphiphilic Metal Complexes in Mesoscopic Phase
| Project/Area Number |
07640752
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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 |
Inorganic chemistry
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| Research Institution | Nara Women's University |
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Principal Investigator |
IIDA Masayasu Department Chemistry, Nara Women's University, Professor, 理学部, 教授 (00107343)
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| Project Period (FY) |
1995 – 1996
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| Keywords | micellar system / NMR relaxations / lyotropic mesophase / self-association / spectrum splitting / selective interaction / vapor pressure depression |
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| Research Abstract |
We have studied microdynamics and interactions of amphiphilic cobalt (III), chromium (III), and zinc (II) complexes in micellar and liquid crystalline systems. The complexes studied are electrolytes and therefore their interactions are in principle governed by electrostatic forces. However, netal complexes having specific sites in their molecular structures showed various weak and selective interactions. Furthermore, the interactions occur in mesoscopic (nano meter scale) region, where the time scale of the motions of complex ions is almost in the range of nano second order. In these systems, NMR relaxation methods were very useful and gave much information concerning the microscopic interactions for the complex ions and their counterions with surfactants.
The contents of the studies are mainly composed of the following three subjects. 1 Specific interactions between metal complex ions and surfactants were monitored by ^<59>Co NMR spectroscopies for the complex ions and paramagnetic chr
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omium (III) -induced ^<13>C relaxations for the carbon atoms of surfactants in micellar systems. It was characteristic that ^<59>Co NMR peak for [Co(chxn)_3]^<3+> shifts to downfield by the interaction with sulfate and sulfonate surfactants while it does to upfield by the interaction with carboxylate surfactant. The positions of [Cr(en)_3]^<3+> and [Cr(chxn)_3]^<3+> in micelles are at the headgroup sites while that of [Cr(phen)_3]^<3+> is in hydrocarbon cores of micelles. 2 The selective interactions between [Co(en)_3]^<3+> enantiomers and chiral surfactants of dodecylamino acids (in micellar and liquid crystalline systems) have been discriminated by ^<59>Co NMR parameters such as chemical shifts, relaxation times, and quadrupole splittings. 3 Cobalt (III) and zinc (II) complexes having alkylethylenediamine ligands were prepared and the process of their self-associations was followed using vapor pressure depression and multinuclear NMR methods. It was revealed that these surfactants form unique morphology of aggregates like reverse micelles because of their unique structures of metal complexes. Less
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