Spectral characterization of self-assemblies of aldopyranoside amphiphilic gelators

What is the essential structural difference between simple amphiphiles and bolaamphiphiles?

Jong Hwa Jung, Seiji Shinkai, Toshimi Shimizu

Research output: Contribution to journalArticle

175 Citations (Scopus)

Abstract

An aldopyranoside-based gelators (dodecanoyl-p-aminophenyl-β-D-aldopyranoside)s and [1,12-dodecanedicarboxylic-bis(p-aminophenyl-β-D-aldopyranoside)]s 1-4 were synthesized, and their gelation ability was evaluated in organic solvents and water. Simple aldopyranoside amphiphiles 1 and 2 were found to gelate organic solvents as well as water in the presence of a small amount of alcoholic solvents. More interestingly, not only extremely dilute aqueous solutions (0.05 wt%) of the bolaamphiphiles 3 and 4, but solutions of 3 and 4 in several organic solvents could be gelatinized. These results indicate that 1-4 can act as versatile amphiphilic gelators. We characterized the superstructures of the aqueous gels and organogels prepared from 1-4 using SEM, TEM, NMR and IR spectroscopy, and XRD. The aqueous gels 1 and 2 formed a three-dimensional network of puckered fibrils diameters in the range 20-200 nm, whereas the aqueous gels 3 and 4 produced filmlike lamellar structures with 50-100 nm thickness at extremely low concentrations (0.05 wt%). Powder XRD experiments indicate that the aqueous gels 1 and 2 maintain an interdigitated bilayer structure with a 2.90 nm period with the alkyl chain tilted, while the organogels 1 and 2 take a loosely interdigitated bilayer structure with a 3.48 nm period. On the other hand, the aqueous- and the organogels 3 and 4 have 3.58 nm spacing, which corresponds to a monolayered structure. The XRD, 1H NMR and FT-IR results suggest that 1-4 are stabilized by a combination of the hydrogen-bonding, φ-φ interactions and hydrophobic forces.

Original languageEnglish
Pages (from-to)2684-2690
Number of pages7
JournalChemistry - A European Journal
Volume8
Issue number12
DOIs
Publication statusPublished - Jun 17 2002

Fingerprint

Amphiphiles
Self assembly
Gels
Organic solvents
Lamellar structures
Water
Gelation
Powders
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Hydrogen bonds
Nuclear magnetic resonance
Transmission electron microscopy
Scanning electron microscopy
bolaamphiphile
Experiments

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Spectral characterization of self-assemblies of aldopyranoside amphiphilic gelators : What is the essential structural difference between simple amphiphiles and bolaamphiphiles? / Jung, Jong Hwa; Shinkai, Seiji; Shimizu, Toshimi.

In: Chemistry - A European Journal, Vol. 8, No. 12, 17.06.2002, p. 2684-2690.

Research output: Contribution to journalArticle

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abstract = "An aldopyranoside-based gelators (dodecanoyl-p-aminophenyl-β-D-aldopyranoside)s and [1,12-dodecanedicarboxylic-bis(p-aminophenyl-β-D-aldopyranoside)]s 1-4 were synthesized, and their gelation ability was evaluated in organic solvents and water. Simple aldopyranoside amphiphiles 1 and 2 were found to gelate organic solvents as well as water in the presence of a small amount of alcoholic solvents. More interestingly, not only extremely dilute aqueous solutions (0.05 wt{\%}) of the bolaamphiphiles 3 and 4, but solutions of 3 and 4 in several organic solvents could be gelatinized. These results indicate that 1-4 can act as versatile amphiphilic gelators. We characterized the superstructures of the aqueous gels and organogels prepared from 1-4 using SEM, TEM, NMR and IR spectroscopy, and XRD. The aqueous gels 1 and 2 formed a three-dimensional network of puckered fibrils diameters in the range 20-200 nm, whereas the aqueous gels 3 and 4 produced filmlike lamellar structures with 50-100 nm thickness at extremely low concentrations (0.05 wt{\%}). Powder XRD experiments indicate that the aqueous gels 1 and 2 maintain an interdigitated bilayer structure with a 2.90 nm period with the alkyl chain tilted, while the organogels 1 and 2 take a loosely interdigitated bilayer structure with a 3.48 nm period. On the other hand, the aqueous- and the organogels 3 and 4 have 3.58 nm spacing, which corresponds to a monolayered structure. The XRD, 1H NMR and FT-IR results suggest that 1-4 are stabilized by a combination of the hydrogen-bonding, φ-φ interactions and hydrophobic forces.",
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