Large-scale Porphyrin Assemblies - Function Control via. Self-assembling Processes
Grant-in-Aid for Scientific Research (B)
|Allocation Type||Single-year Grants|
Chemistry related to living body
|Research Institution||Kyoto Institute of Technology|
KURODA Yasuhisa Kyoto Institute of Technology, Department of Polymer Science and Engineering, Professor, 繊維学部, 教授 (00111930)
|Project Period (FY)
2003 – 2005
Completed(Fiscal Year 2005)
|Budget Amount *help
¥15,300,000 (Direct Cost : ¥15,300,000)
Fiscal Year 2005 : ¥1,300,000 (Direct Cost : ¥1,300,000)
Fiscal Year 2004 : ¥2,700,000 (Direct Cost : ¥2,700,000)
Fiscal Year 2003 : ¥11,300,000 (Direct Cost : ¥11,300,000)
|Keywords||Porphyrin / self assembly / energy transfer / cyclodextrin / 光合成 / 電荷分離|
Following three types of large-scale porphyrin assemblies were investigated.
1. Antenna model systems assembled on the pyrazine recognition sites.
A series of assemblies having antenna porphyrins at various distances from energy acceptor porphyrin has been constructed. Both static and dynamic aspects of the energy transfer in these assemblies ware confirmed to agree with the theoretical expectation of the Forster mechanism quantitatively. The assembling processes itself for the antenna systems which have antenna porphyrins serially arranged on an alkyl chain were shown to obey the "one after another" mechanism by using newly developed kinetic analyses program for multi differential equations.
2. Specific cyclic porphyrin assemblies using cyclodextrin inclusion in an aqueous solution
The porphyrin or biphenyl linked oligomers of permethylcyclodextrin were demonstrated to give unique cyclic porphyrin assemblies specifically. These water soluble assemblies constructed by using Zn and free base porphyrins shows the intramolecular energy transfer reaction. Furthermore, the assembly constructed on the Zn porphyrin linked oligomer was shown to form a large bidentate coordination space, which selectively recognizes the bis-pyridine ligand having ca. 20 Å of N-N distance of pyridine moieties.
3. Porphyrin aggregates sensitive to environmental solvent compositions.
Tetrakis-(p-sulfonatophenyl)porphyrin having hydrophobic counter ions, TPPS・C8, shows unique aggregation formation behavior. This porphyrins forms very large aggregation, ca. 100 nm of hydrodynamic diameter, in the mixed solvent of MeOH / CH_2Cl_2 (v/v) = 0.1-02, which is assigned as the H-type aggregate judging from their blue-shifted absorption. In addition, only MgTPPS・C8 is shown to forms small J-type aggregate in pure CH_2Cl_2, in which the sulfonato group mutually coordinates on the Mg atom.
Research Products (15results)