Hostname: page-component-76d6cb85b7-f97m6 Total loading time: 0 Render date: 2026-07-25T00:23:14.876Z Has data issue: false hasContentIssue false
  • English
  • Français

Adsorption and stacking behaviour of zwitterionic porphyrin on the clay surface†

Published online by Cambridge University Press:  09 July 2018

T. Eyama ,
Y. Yogo ,
T. Fujimura ,
T. Tsukamoto ,
D. Masui ,
T. Shimada ,
H. Tachibana ,
H. Inoue  and
S. Takagi
T. Eyama
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
Y. Yogo
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
T. Fujimura
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
T. Tsukamoto
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
D. Masui
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
T. Shimada
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
H. Tachibana
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
H. Inoue
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan
S. Takagi*
Affiliation:
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, Japan PRESTO (Precursory Research for Embryonic Science and Technology), Japan Science and Technology Agency, 4-1-8 Honcho Kawaguchi, Saitama, Japan
*
*E-mail: takagi-shinsuke@tmu.ac.jp
Get access Rights & Permissions [Opens in a new window]

Abstract

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.

Keywords

montmorillonitezwitterionic porphyrinelectrostatic interactionorganic dyesize-matching rule

Information

Type
Research Papers
Information
Clay Minerals , Volume 47 , Issue 2 , June 2012 , pp. 243 - 250
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2012

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

Footnotes

†

Presented at the Euroclay 2011 Conference at Antalya, Turkey

References

Chernia, Z. & Gill, D. (1999) Flattening of TMPyP adsorbed on Laponite. Evidence in observed and caluculated UV-vis spectra. Langmuir, 15, 1625–1633.Google Scholar
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.Google Scholar
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.Google Scholar
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.CrossRefGoogle Scholar
Kasha, M., Rawls, H. R. & Ashraf El-Bayoumi, M. (1965) The exciton model in molecular spectroscopy. Pure and Applied Chemistry, 11, 371–392.Google Scholar
Kuykendall, V. G. & Thomas, J. K. (1990) Photophysical investigation of the degree of dispersion of aqueous colloidal clay. Langmuir, 6, 1350–1356.Google Scholar
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.Google Scholar
Maruyama, K. & Osuka, A. (1990) A chemical approach toward photosynthetic reaction center. Pure and Applied Chemistry, 62, 1511–1520.CrossRefGoogle Scholar
Ogawa, M. & Kuroda, K. (1995) Photofunctions of intercalation compounds. Chemical Reviews, 95, 399–438.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.Google Scholar
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.CrossRefGoogle Scholar