A pH-responsive carboxylic β-1,3-glucan polysaccharide for complexation with polymeric guests

Le Thi Ngoc Lien, Tomohiro Shiraki, Arnab Dawn, Youichi Tsuchiya, Daisuke Tokunaga, Shun Ichi Tamaru, Naoya Enomoto, Junichi Hojo, Seiji Shinkai

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24 Citations (Scopus)

Abstract

The helix-forming nature of β-1,3-glucan polysaccharides is a characteristic that has potential for producing gene carriers, bio-nanomaterials and other chiral nanowires. Herein, carboxylic curdlan (CurCOOH) bearing the β-1,3-polyglucuronic acid structure was successfully prepared from β-1,3-glucan polysaccharide curdlan (Cur) by one-step oxidation using a 4-acetamido-TEMPO/NaClO/NaClO2 system as the oxidant. The resulting high-molecular-weight CurCOOH was proved to bear the 6-COOH group in 100% purity. The optical rotatory dispersion (ORD) spectra indicated that the obtained CurCOOH behaves as a water-soluble single-strand in various pH aqueous media. This advantage has allowed us to use CurCOOH as a polymeric host to form various macromolecular complexes. For example, complexation of CurCOOH with single-walled carbon nanotubes (SWNTs) resulted in a water-soluble one-dimensional architecture, which formed a dispersion in aqueous solution that was stable for several months, and much more stable than SWNTs complexes of the similar negatively-charged polyacrylic acid (PAA) and polymethacrylic acid (PMAA). It was shown that in the complex, SWNTs are effectively wrapped by a small amount of CurCOOH, enabling them to avoid electrostatic repulsion. This pH-responsive CurCOOH formed a very stable complex with cationic water-soluble polythiophenes (PT-1), which was stabilized not only by the hydrophobic interaction but also by the electrostatic attraction between trimethylammonium cations in PT-1 and dissociated anionic COO- groups in CurCOOH. The included PT-1 became CD-active only in the neutral to basic pH region, and the positive Cotton effect suggested that the conjugated main chain is twisted in the right-handed direction. We also found that CurCOOH can interact with polycytidylic acid (poly(C)) only under high NaCl concentrations, the binding and release of which could be controlled by a change in the salt concentration. We believe, therefore, that CurCOOH bearing a dissociable COOH group can act as a new potential polymeric host to construct novel polymeric complexes applicable for gene carriers, biosensors, chiral polymer assemblies, etc.

Original languageEnglish
Pages (from-to)4266-4275
Number of pages10
JournalOrganic and Biomolecular Chemistry
Volume9
Issue number11
DOIs
Publication statusPublished - Jun 7 2011

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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    Lien, L. T. N., Shiraki, T., Dawn, A., Tsuchiya, Y., Tokunaga, D., Tamaru, S. I., Enomoto, N., Hojo, J., & Shinkai, S. (2011). A pH-responsive carboxylic β-1,3-glucan polysaccharide for complexation with polymeric guests. Organic and Biomolecular Chemistry, 9(11), 4266-4275. https://doi.org/10.1039/c1ob05114h