Giant amino acids designed on the polysaccharide scaffold and their protein-like structural interconversion.

Amphoteric β-1,3-glucans possessing both amino groups and carboxylic acid groups on the C6 positions of glucose units were designed and synthesized from naturally produced curdlan. The amphoteric polysaccharides showed the isoelectric point and the pH responsive interconversion between the original triple helix and single-stranded random structures. Since the pH dependences are comparable to the typical properties of proteins, the polysaccharides can be considered as a new class of giant amino acids. Utilizing the pH responsiveness, pH-controlled catch-and-release has been realized for cationic peptides or anionic DNA. We believe that the amphoteric polysaccharide can act as a new potential polymer to construct stimuli-responsive smart materials on the basis of the polysaccharide scaffold.

[1]  Sayaka Hirano,et al.  Self-assembled pH-sensitive cholesteryl pullulan nanogel as a protein delivery vehicle. , 2013, Biomacromolecules.

[2]  Astrid Gräslund,et al.  Efficient intracellular delivery of nucleic acid pharmaceuticals using cell-penetrating peptides. , 2012, Accounts of chemical research.

[3]  K. Choi,et al.  Sticky nanoparticles: a platform for siRNA delivery by a bis(zinc(II) dipicolylamine)-functionalized, self-assembled nanoconjugate. , 2012, Angewandte Chemie.

[4]  Svetlana Sukhishvili,et al.  Polymer assemblies for controlled delivery of bioactive molecules from surfaces. , 2011, Advanced drug delivery reviews.

[5]  S. Tamaru,et al.  Heat and light dual switching of a single-walled carbon nanotube/thermo-responsive helical polysaccharide complex: a new responsive system applicable to photodynamic therapy. , 2011, Chemical communications.

[6]  S. Tamaru,et al.  A pH-responsive carboxylic β-1,3-glucan polysaccharide for complexation with polymeric guests. , 2011, Organic & biomolecular chemistry.

[7]  K. Akiyoshi,et al.  Amphiphilic polysaccharide nanoballs: a new building block for nanogel biomedical engineering and artificial chaperones. , 2011, ACS nano.

[8]  S. Shinkai,et al.  Thermo- and solvent-responsive polymer complex created from supramolecular complexation between a helix-forming polysaccharide and a cationic polythiophene. , 2010, Journal of the American Chemical Society.

[9]  S. Shinkai,et al.  Semiartificial Polysaccharide Can Provide a Unique Nanospace for the Construction of Supramolecular Dye-assembly , 2010 .

[10]  S. Harding,et al.  Polysaccharide drug delivery systems based on pectin and chitosan , 2010, Biotechnology & genetic engineering reviews.

[11]  P. Michaud,et al.  Production and characterization of new families of polyglucuronic acids from TEMPO-NaOCl oxidation of curdlan. , 2009, International journal of biological macromolecules.

[12]  S. Shinkai,et al.  Control of polythiophene redox potentials based on supramolecular complexation with helical schizophyllan. , 2009, Chemical communications.

[13]  S. Shinkai,et al.  Quantum dots arrangement and energy transfer control via charge-transfer complex achieved on poly(phenylene ethynylene)/schizophyllan nanowires. , 2009, Chemistry, an Asian journal.

[14]  M. Wada,et al.  TEMPO-mediated oxidation of (1 → 3)-β-d-glucans , 2009 .

[15]  H. Tajalli,et al.  Effects of surfactants on the molecular aggregation of rhodamine dyes in aqueous solutions. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[16]  Patrick Keller,et al.  Stimuli-responsive polymer vesicles , 2009 .

[17]  S. Shinkai,et al.  Hierarchical carbon nanotube assemblies created by sugar-boric or boronic acid interactions. , 2008, Chemical communications.

[18]  C. McCormick,et al.  Advances in the synthesis of amphiphilic block copolymers via RAFT polymerization: stimuli-responsive drug and gene delivery. , 2008, Advanced drug delivery reviews.

[19]  S. Shinkai,et al.  Creation of hierarchical carbon nanotube assemblies through alternative packing of complementary semi-artificial beta-1,3-glucan/carbon nanotube composites. , 2008, Chemistry.

[20]  K. Sakurai,et al.  Polysaccharide‐templated twisted assemble of 2‐anilinonaphthalene‐6‐sulfonic acid , 2008 .

[21]  M. Ikeda,et al.  Controlled stability of the triple-stranded helical structure of a beta-1,3-glucan with a chromophoric aromatic moiety at a peripheral position. , 2007, Chemistry, an Asian journal.

[22]  K. Sakurai,et al.  Complex formation between cationic beta-1,3-glucan and hetero-sequence oligodeoxynucleotide and its delivery into macrophage-like cells to induce cytokine secretion. , 2007, Organic & biomolecular chemistry.

[23]  S. Shinkai,et al.  New approach to preparing one-dimensional Au nanowires utilizing a helical structure constructed by schizophyllan , 2007 .

[24]  T. Takeya,et al.  Induction of cell death by photodynamic therapy with water-soluble lipid-membrane-incorporated [60]fullerene. , 2007, Organic & biomolecular chemistry.

[25]  K. Sakurai,et al.  Instantaneous inclusion of a polynucleotide and hydrophobic guest molecules into a helical core of cationic beta-1,3-glucan polysaccharide. , 2007, Journal of the American Chemical Society.

[26]  K. Sakurai,et al.  β-1,3-Glucan (Schyzophyllan) Can Act as a One-Dimensional Host for Creating Chirally Twisted Poly(p-phenylene Ethynylene) , 2007 .

[27]  D. Schmaljohann.  Thermo- and pH-responsive polymers in drug delivery. , 2006, Advanced drug delivery reviews.

[28]  Kevin B. Hicks,et al.  Pectin in controlled drug delivery – a review , 2006 .

[29]  Chun Xing Li,et al.  Beta-1,3-glucan polysaccharide (schizophyllan) acting as a one-dimensional host for creating supramolecular dye assemblies. , 2006, Organic letters.

[30]  S. Shinkai,et al.  6-Amino-6-deoxy-chitosan. Sequential chemical modifications at the C-6 positions of N-phthaloyl-chitosan and evaluation as a gene carrier. , 2006, Carbohydrate research.

[31]  K. Sakurai,et al.  CpG DNA/zymosan complex to enhance cytokine secretion owing to the cocktail effect. , 2006, Bioorganic & medicinal chemistry letters.

[32]  Chun Xing Li,et al.  'Click chemistry' on polysaccharides: a convenient, general, and monitorable approach to develop (1-->3)-beta-D-glucans with various functional appendages. , 2005, Carbohydrate research.

[33]  Chun Xing Li,et al.  Beta-1,3-glucan polysaccharides as novel one-dimensional hosts for DNA/RNA, conjugated polymers and nanoparticles. , 2005, Chemical communications.

[34]  Y. Iwasaki,et al.  Hybrid nanogels with physical and chemical cross-linking structures as nanocarriers. , 2005, Macromolecular bioscience.

[35]  K. Sakurai,et al.  Inclusion of cut and as-grown single-walled carbon nanotubes in the helical superstructure of schizophyllan and curdlan (beta-1,3-glucans). , 2005, Journal of the American Chemical Society.

[36]  K. Sakurai,et al.  Beta-1,3-glucan (schizophyllan) can act as a one-dimensional host for creation of novel poly(aniline) nanofiber structures. , 2004, Organic letters.

[37]  K. Sakurai,et al.  Curdlan and schizophyllan (β-1,3-glucans) can entrap single-wall carbon nanotubes in their helical superstructure , 2004 .

[38]  T. Uryu,et al.  Synthesis and anti-HIV activity of ­6-amino-6-deoxy-(1→3)-β-D-curdlan sulfate† , 2003 .

[39]  M. Linial,et al.  Polysaccharide-oligoamine based conjugates for gene delivery. , 2002, Journal of medicinal chemistry.

[40]  K. Sakurai,et al.  Polysaccharide--polynucleotide complexes. 2. Complementary polynucleotide mimic behavior of the natural polysaccharide schizophyllan in the macromolecular complex with single-stranded RNA and DNA. , 2001, Biomacromolecules.

[41]  S. Shinkai,et al.  Molecular Recognition of Adenine, Cytosine, and Uracil in a Single-Stranded RNA by a Natural Polysaccharide: Schizophyllan , 2000 .

[42]  H. Fujita,et al.  Triple Helix of Schizophyllum commune Polysaccharide in Dilute Solution. 3. Hydrodynamic Properties in Water , 1980 .

[43]  R. Marchessault,et al.  Triple-Helical Structure of(1→3)-β-D-Glucan , 1980 .

[44]  B. Sathyanarayana,et al.  Conformational Studies of β‐glucans , 1971 .

[45]  B. Sumerlin,et al.  Future perspectives and recent advances in stimuli-responsive materials , 2010 .

[46]  K. Sakurai,et al.  Click Chemistry on Curdlan: A Regioselective and Quantitative Approach to Develop Artificial β-1,3-Glucans with Various Functional Appendages , 2006 .