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Adsorption and stacking behaviour of zwitterionic porphyrin on the clay surface

  • T. Eyama (a1), Y. Yogo (a1), T. Fujimura (a1), T. Tsukamoto (a1), D. Masui (a1), T. Shimada (a1), H. Tachibana (a1), H. Inoue (a1) and S. Takagi (a1) (a2)...


Zwitterionic porphyrin (tetrakis {4-(2-carboxyethyl)pyridinio}porphyrin (TPyCP)) with four pyridinium and carboxyl groups in the molecule was synthesized. The adsorption behaviour of TPyCP on the montmorillonite clay surface was examined in an aqueous colloidal solution. While the adsorption maximum λmax of TPyCP was 424 nm in water, it shifted to longer wavelengths on complex formation with clay. The λmax on the exfoliated clay surface was 450 nm, and that in the stacked clay sheets was 471 nm, respectively. Under alkaline conditions ([NaOH] = 2 × 10–4 M), the stacking behaviour of the clay was completely suppressed. It emerged that anionic parts in the porphyrin molecule can suppress the stacking of clay sheets. Judging from the quantitative analysis, the maximum adsorption amount of TPyCP was 100% vs. cation exchange capacity (CEC) of the clay. As the adsorption density of TPyCP increased, λmax shifted slightly to longer wavelengths due to the interactions between adjacent porphyrins. When the loading level of TPyCP was 200% vs. CEC, the stacking of TPyCP was indicated. The average stacking layer number was calculated to be 1.48. On the other hand, it is known that tetra cationic porphyrins without anionic parts do not form such stacking structures. Thus, it seems that zwitterionic porphyrin has the potential to form a three dimensional structure through electrostatic interactions between porphyrins on the clay surface.


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Presented at the Euroclay 2011 Conference at Antalya, Turkey



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Chernia, Z. & Gill, D. (1999) Flattening of TMPyP adsorbed on Laponite. Evidence in observed and caluculated UV-vis spectra. Langmuir, 15, 1625–1633.
Egawa, T., Watanabe, H., Fujimura, T., Ishida, Y., Yamato, M., Masui, D., Shimada, T., Tachibana, H., Yoshida, H., Inoue, H. & Takagi, S. (2011) Novel methodology to control the adsorption structure of cationic porphyrin on the clay surface using the “Size- Matching Rule”. Langmuir, 27, 10722–10729.
Inoue, H., Funyu, S., Shimada, Y. & Takagi, S. (2005) Artificial photosynthesis via two-electron conversion: Photochemical oxygenation sensitized by ruthenium porphyrins with water as both electron and oxygen donor. Pure and Applied Chemistry, 77, 1019–1033.
Ishida, Y., Shimada, T., Masui, D., Tachibana, H., Inoue, H. & Takagi, S. (2011) Efficient excited energy transfer reaction in clay/porphyrin complex toward an artificial Light-Harvesting System. Journal of the American Chemical Society, 133, 14280–14286.
Kasha, M., Rawls, H. R. & Ashraf El-Bayoumi, M. (1965) The exciton model in molecular spectroscopy. Pure and Applied Chemistry, 11, 371–392.
Kuykendall, V. G. & Thomas, J. K. (1990) Photophysical investigation of the degree of dispersion of aqueous colloidal clay. Langmuir, 6, 1350–1356.
McDermott, G., Prince, S.M. Freer, A.A., Hawthornthwaite-Lawless, A.M., Papiz, M.Z., Cogdell, R. J. & Isaacs, N. W. (1995) Crystal structure of an integral membrane light-harvesting complex from photosynthetic bacteria. Nature, 345, 517–521.
Maruyama, K. & Osuka, A. (1990) A chemical approach toward photosynthetic reaction center. Pure and Applied Chemistry, 62, 1511–1520.
Ogawa, M. & Kuroda, K. (1995) Photofunctions of intercalation compounds. Chemical Reviews, 95, 399–438.
Takagi, K., Harata, E., Shichi, T., Kanoh, T. & Sawaki, Y. (1997) Intercalation and control of the Norrish type reactions of aromatic ketocarboxylates in hydrotalcite clay interlayers. Journal of Photochemistry and Photobiology A: Chemistry, 105, 47–54.
Takagi, S., Shimada, T., Yui, T. & Inoue, H. (2001) High density adsorption of porphyrins onto clay layer without aggregation: Characterization of smectitecationic porphyrin complex. Chemistry Letters, 30, 128–129.
Takagi, S., Shimada, T., Eguchi, M., Yui, T., Yoshida, H., Tryk, D. A. & Inoue, H. (2002) High-density adsorption of cationic porphyrins on clay layer surgaces without aggregation: The size-matching effect. Langmuir, 18, 2265–2272.
Takagi, S., Eguchi, M., Trynk, D.A & Inoue, H. (2006) Porphyrin photochemistry in inorganic/organic hybrid materials: Clays, layered semiconductors, nanotubes, and mesoporous materials. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 7, 104–126.
Takagi, S., Aratake, Y., Konno, S., Masui, D., Shimada, T. Tachibana, H. & Inoue, H. (2011) Effects of porphyrin structure on the complex formation behavior with clay. Microporous and Mesoporous Materials, 141, 38–42.


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Adsorption and stacking behaviour of zwitterionic porphyrin on the clay surface

  • T. Eyama (a1), Y. Yogo (a1), T. Fujimura (a1), T. Tsukamoto (a1), D. Masui (a1), T. Shimada (a1), H. Tachibana (a1), H. Inoue (a1) and S. Takagi (a1) (a2)...


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