Hostname: page-component-7c8c6479df-nwzlb Total loading time: 0 Render date: 2024-03-29T06:29:56.970Z Has data issue: false hasContentIssue false

Functional organogels from lipophilic L-glutamide derivative immobilized on cyclotriphosphazene core

Published online by Cambridge University Press:  01 May 2006

Tomohiro Shirosaki
Affiliation:
Department of Applied Chemistry and Biochemistry, Kumamoto University, Kumamoto 860-8555, Japan
Saleh Chowdhury
Affiliation:
Department of Applied Chemistry and Biochemistry, Kumamoto University, Kumamoto 860-8555, Japan
Makoto Takafuji
Affiliation:
Department of Applied Chemistry and Biochemistry, Kumamoto University, Kumamoto 860-8555, Japan
Dzhamil Alekperov
Affiliation:
Mendeleyev University of Chemical Technology of Russia, Moscow 125047, Russia
Galina Popova
Affiliation:
Mendeleyev University of Chemical Technology of Russia, Moscow 125047, Russia
Hiroshi Hachisako
Affiliation:
Department of Applied Chemistry, Sojo University, Kumamoto 860-0082, Japan
Hirotaka Ihara*
Affiliation:
Department of Applied Chemistry and Biochemistry, Kumamoto University, Kumamoto 860-8555, Japan
*
a) Address all correspondence to this author. e-mail: ihara@kumamoto-u.ac.jp
Get access

Abstract

A novel cyclotriphosphazene-based low-molecular weight organogelator was prepared by immobilization of six dialkylated L-glutamide derivatives on a cyclotriphosphazene core, and its ability as a self-assembling organogelator was investigated. The organogelator exhibited enhanced gelation ability and chirality, and thixotropic property for self-restoring to a gel state; this was compared to the corresponding L-glutamide-derived organogelator without the core. The gelation test, transmission electron microscopy observation, and circular dichroism (CD) spectral study showed that the gelation and aggregation ability were enhanced by immobilization onto the cyclotriphosphazene core. Gels in chloroform and cyclohexane-ethanol (95:5) mixture showed an unusual thixotropic property.

Type
Articles
Copyright
Copyright © Materials Research Society 2006

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.)

References

REFERENCES

1.Allcock, H.R.: Phosphorus-Nitrogen Compounds (Academic Press, New York, 1972).Google Scholar
2.Caminade, A., Majoral, J.: Synthesis of phosphorus-containing macrocycles and cryptands. Chem. Rev. 94, 1183 (1994).CrossRefGoogle Scholar
3.Moriya, K., Suzuki, T., Mizusaki, H., Yano, S., Kajiwara, M.: Liquid crystalline phase transition in organophosphazenes with 4-octyloxybiphenyl mesogenic groups. Chem. Lett. (Jpn.) 10, 1001 (1997).CrossRefGoogle Scholar
4.Inoue, K., Itaya, T.: Synthesis and functionality of cyclophosphazene-based polymers. Bull. Chem. Soc. Jpn. 74, 1381 (2001).CrossRefGoogle Scholar
5.Inoue, K., Sakai, H., Ochi, S., Itaya, T., Tanigaki, T.: Preparation and conformation of hexaarmed star poly(β-benzyl-L-aspartates) synthesized utilizing hexakis(4-aminophenoxy) cyclotriphosphazene. J. Am. Chem. Soc. 116, 10783 (1994).CrossRefGoogle Scholar
6.Allcock, H., Kwon, S.: An ionically crosslinkable polyphosphazene: Poly[bis(carboxylatophenoxy)phosphazene] and its hydrogels and membranes. Macromolecules 22, 75 (1989).CrossRefGoogle Scholar
7.Neilson, R., Neilson, P.: Poly(alkyl/arylphosphazenes) and their precursors. Chem. Rev. 88, 541 (1988).CrossRefGoogle Scholar
8.Sengupta, S.: A ferrocene dendrimer based on a cyclotriphosphazene core. Tetrahedron Lett. 44, 7281 (2003).CrossRefGoogle Scholar
9.Sengupta, S.: A hexaferrocenyl cluster based on a cyclotriphosphazene core: Synthesis and electrochemistry. Polyhedron 22, 1237 (2003).CrossRefGoogle Scholar
10.Moriya, K., Kawanishi, Y., Yano, S., Kajiwara, M.: Mesomorphic phase transition of a cyclotetraphosphazene containing Schiff base moieties: Comparison with the corresponding cyclotriphosphazene. Chem. Commun. 13, 1111 (2000).CrossRefGoogle Scholar
11.Terech, P., Weiss, R.: Low molecular mass gelators of organic liquids and the properties of their gels. Chem. Rev. 97, 3133 (1997).CrossRefGoogle ScholarPubMed
12.Esch, J., Feringa, B.: New functional materials based on self-assembling organogels: From serendipity towards design. Angew. Chem. Int. Ed. Engl. 39, 2263 (2000).3.0.CO;2-V>CrossRefGoogle Scholar
13.Ihara, H., Takafuji, M., Sakurai, T. Self-assembled nanofibers, in Encyclopedia of Nanoscience and Nanotechnology, edited by Nalwa, H.S. (American Scientific Publishers, Stevenson Ranch, CA, 2004), Vol. 9, p. 473.Google Scholar
14.Oda, R. SAFIN gels with amphiphilic molecules, in Molecular Gels. Materials with Self-Assembled Fibrillar Networks, edited by Weiss, R.G. and Terech, P. (Springer, Berlin, 2005), p. 575.Google Scholar
15.Shimizu, T., Masuda, M., Minamikawa, H.: Supramolecular nanotube architectures based on amphiphilic molecules. Chem. Rev. 105, 1401 (2005).CrossRefGoogle ScholarPubMed
16.Gronwald, O., Snip, E., Shinkai, S.: Gelators for organic liquids based on self-assembly: A new facet of supramolecular and combinatorial chemistry. Curr. Opin. Colloid Interface Sci. 7, 148 (2002).CrossRefGoogle Scholar
17.Allcock, H., Bender, J., Morford, R., Berda, E.: Synthesis and characterization of novel solid polymer electrolytes based on poly(7-oxanorbornenes) with pendent oligoethyleneoxy-functionalized cyclotriphosphazenes. Macromoleculs 36, 3563 (2003).CrossRefGoogle Scholar
18.Ihara, H., Hachisako, H., Hirayama, C., Yamada, K.: Lipid membrane analogues, formation of highly-oriented structures and their phase separation behavior in benzene. J. Chem. Soc. Chem. Commun. 17, 1244 (1992).CrossRefGoogle Scholar
19.Ihara, H., Yoshitake, M., Takafuji, M., Yamada, T., Sagawa, T., Hirayama, C.: Detection of highly-oriented aggregation of L-glutamic acid-derived lipids in organic solution. Liq. Cryst. 26, 1021 (1999).CrossRefGoogle Scholar
20.Kunitake, T., Nakashima, N., Shimomura, M., Okahata, Y., Kano, K., Ogawa, T.: Unique properties of chromophore-containing bilayer aggregates: Enhanced chirality and photochemically induced morphological change. J. Am. Chem. Soc. 102, 6642 (1980).CrossRefGoogle Scholar
21.Nakashima, N., Fukushima, H., Kunitake, T.: Large induced circular dichroism of methyl orange bound to chiral bilayer membranes. Its extreme sensitivity to the phase transition and the chemical structure of the membrane. Chem. Lett. (Jpn.). 9, 1207 (1981).CrossRefGoogle Scholar
22.Ihara, H., Hachisako, H., Hirayama, C., Yamada, K.: Amphiphiles with polypeptide-head groups. V. Specific bindings of methyl orange to chiral bilayer membranes with β-alanyl-L-glutamoyl head groups. Liq. Cryst. 2, 215 (1987).CrossRefGoogle Scholar
23.Ihara, H., Takafuji, M., Hirayama, C., O'Brien, D.F.: Effect of photopolymerization on the morphology of helical supramolecular assemblies. Langmuir 8, 1548 (1992).CrossRefGoogle Scholar
24.Lescanne, M., Grondin, P., d’Aléo, A., Fages, F., Pozzo, J.L., Monval, O., Reinheimer, P., Colin, A.: Thixotropic organogels based on a simple n-hydroxyalkyl amide: Rheological and aging properties. Langmuir 20, 3032 (2004).CrossRefGoogle ScholarPubMed
25.Loiseau, J., Lescanne, M., Colin, A., Fages, F., Verlhac, J., Vincent, J.: A fluoroponytails containing organogelator: Gelation of perfluorotributylamine and isopropanol. Tetrahedron 58, 4049 (2002).CrossRefGoogle Scholar
26.Brinksma, J., Feringa, B., Kellog, R., Vreeker, R., Esch, J.: Rheology and thermotropic properties of bis-urea-based organogels in various primary alcohols. Langmuir 16, 9249 (2000).CrossRefGoogle Scholar