Thermo- and solvent-responsive polymer complex created from supramolecular complexation between a helix-forming polysaccharide and a cationic polythiophene

Tomohiro Shiraki, Arnab Dawn, Youichi Tsuchiya, Seiji Shinkai

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

The helical structure is one of key structural components for both biological systems and artificial chiral systems. So far, we have succeeded in fabricating "tight" insulated molecular wires consisting of a triple-stranded cohelical structure formed through supramolecular wrapping of synthetic polymers by a helix-forming polysaccharide (schizophyllan). Herein, we have designed a new modified polysaccharide (Cur-oeg) to form a "loose" macromolecular complex with a conjugated polymer (CP) that allows structural changes in response to external stimuli. Cur-oeg forms a helical complex with an achiral cationic polythiophene (PT1), and the effective conjugation length is changed by temperature, showing a large absorption peak shift from 403 to 482 nm between 85 and 5 °C. According to the change in the conjugation system, the fluorescence and the induced circular dichroism show the continuous spectral shifts under temperature control. The color changes in the absorption and the fluorescence are detectable with observation by the naked eye and are reversibly controlled under thermal cycles, indicating that this system has the function of a "molecular thermometer". It is shown that the induced thermoresponsiveness is associated with structural rearrangement of the helical conformation of PT1 in the complex. Moreover, another unique responsiveness is discovered for the film state: that is, the film color is varied when it is exposed to the vapor of water or methanol (vaporchromism), resulting from the structural change of PT1 occurring even in the film state. These flexible molecular motions in both the solution state and the film state can be applicable to the design of CP-based smart sensors, polarized materials, switching devices, etc.

Original languageEnglish
Pages (from-to)13928-13935
Number of pages8
JournalJournal of the American Chemical Society
Volume132
Issue number39
DOIs
Publication statusPublished - Oct 6 2010

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Polysaccharides
Complexation
Polymers
Conjugated polymers
Sizofiran
Color
Fluorescence
Color films
Macromolecular Substances
Thermometers
Smart sensors
Temperature
Steam
Dichroism
Biological systems
Circular Dichroism
Temperature control
Methanol
Conformations
Hot Temperature

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Thermo- and solvent-responsive polymer complex created from supramolecular complexation between a helix-forming polysaccharide and a cationic polythiophene. / Shiraki, Tomohiro; Dawn, Arnab; Tsuchiya, Youichi; Shinkai, Seiji.

In: Journal of the American Chemical Society, Vol. 132, No. 39, 06.10.2010, p. 13928-13935.

Research output: Contribution to journalArticle

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