Kazuo Sakurai

Molecular Dynamics Studies of Side Chain Effect on the β-1,3-d-Glucan Triple Helix in Aqueous Solution

beta-1,3-D-glucans have been isolated from fungi as right-handed 6(1) triple helices. They are categorized by the side chains bound to the main triple helix through beta-(1-->6)-D-glycosyl linkage. Indeed, since a glucose-based side chain is water soluble, the presence and frequency of glucose-based side chains give rise to significant variation in the physical properties of the glucan family. Curdlan has no side chains and self-assembles to form an water-insoluble triple helical structure, while schizophyllan, which has a 1,6-D-glucose side chain on every third glucose unit along the main chain, is completely water soluble. A thermal fluctuation in the optical rotatory dispersion is observed for the side chain, indicating probable co-operative interaction between the side chains and water molecules. This paper documents molecular dynamics simulations in aqueous solution for three models of the beta-1,3-D-glucan series: curdlan (no side chain), schizophyllan (a beta-(1-->6)-D-glycosyl side-chain at every third position), and a hypothetical triple helix with a side chain at every sixth main-chain glucose unit. A decrease was observed in the helical pitch as the population of the side chain increased. Two types of hydrogen bonding via water molecules, the side chain/main chain and the side chain/side chain hydrogen bonding, play an important role in determination of the triple helix conformation. The formation of a one-dimensional cavity of diameter about 3.5 A was observed in the schizophyllan triple helix, while curdlan showed no such cavity. The side chain/side chain hydrogen bonding in schizophyllan and the hypothetical beta-1,3-D-glucan triple helix could cause the tilt of the main-chain glucose residues to the helix.

Single-walled carbon nanotubes acquire a specific lectin-affinity through supramolecular wrapping with lactose-appended schizophyllan.

Single-walled carbon nanotubes can be entrapped within a helical superstructure composed of schizophyllan bearing lactoside-appendages to show an excellent water-solubility as well as a specific lectin-affinity.

β-1,3-Glucan polysaccharide can act as a one-dimensional host to create novel silica nanofiber structures

We have demonstrated that the creation of novel silica nanofibers with a uniform diameter is possible by utilizing beta-1,3-glucan polysaccharide as a one-dimensional host for monoalkoxysilane; the finding establishes that beta-1,3-glucan can act not only as a novel one-dimensional host for metal alkoxide polycondensation but also as an interface between inorganic nanofibers and functional organic molecules.

Schizophyllans carrying oligosaccharide appendages as potential candidates for cell-targeted antisense carrier.

Schizophyllans carrying beta-lactoside and alpha-mannoside appendages were prepared from native schizophyllan through NaIO4 oxidation followed by reductive amination using aminoethyl-beta-lactoside and alpha-mannoside, respectively. The resulting schizophyllans form stable macromolecular complexes with polynucleotides, such as poly(C) and poly(dA). Specific affinity between these macromolecular complexes and saccharide-binding proteins was demonstrated by surface plasmon resonance and agarose gel staining assays. beta-lactoside-appended schizophyllan enhanced an antisense activity in hepatocytes which express lactoside-binding proteins on their cell surfaces.

Poly(diacetylene)-nanofibers can be fabricated through photo-irradiation using natural polysaccharide schizophyllan as a one-dimensional mold.

Schizophyllan interacts with various 1,4-diphenylbutadiyne derivatives to induce their chirally-twisted packing. A series of referential experiments using other polysaccharides (amylose, pullulan, dextran, etc.) and a carbohydrate-appended detergent (dodecyl-beta-d-glucopyranoside) indicates that these 1,4-diphenylbutadiyne derivatives are accommodated within a tubular cavity constructed by a helical superstructure of schizophyllan. In these 1,4-diphenylbutadiyne derivatives, 1,4-bis(p-propionamidophenyl)butadiyne can be easily polymerized through UV-irradiation, in which schizophyllan acts as a one-dimensional mold to produce the corresponding poly(diacetylene)s with fibrous morphologies. Detailed investigations on this unique approach to prepare the nanofibers revealed that it includes two individual processes, that is, 1) UV-mediated polymerization of encapsulated 1,4-bis(p-propionamidophenyl)butadiyne to produce immature nanofibers and 2) their reorganization through hydrophobic interfiber interactions into ordered nanofibers. The other 1,4-diphenylbutadiyne derivatives could not be polymerized through UV-irradiation, indicating that the p-propionamido-functionalities play substantial roles for a suitable packing of the monomer for the polymerization. The other 1,4-diphenylbutadiyne derivatives, however, can be also polymerized through gamma-ray irradiation in the presence of schizophyllan to give the corresponding poly(diacetylene)-nanofibers, emphasizing the wide applicability of the schizophyllan-based strategy for polymerization of various 1,4-diphenylbutadiyne derivatives.

Chiral Supramolecular Gels with Lanthanide Ions: Correlation between Luminescence and Helical Pitch

We report the correlation between the fluorescence intensity and the helical pitch of supramolecular hydrogels with Tb(III) and Eu(III) as well as their inkjet printing patterning as an application. The luminescent gels, which exhibited three different emissions of red, green, and blue, could be prepared without and with Eu(III) and Tb(III). The luminescence intensity of supramolecular gels (gel-Tb and gel-Eu) composed of Tb(III) and Eu(III) was ca. 3-fold larger than that of the sol (1+Tb(III) or 1+Eu(III)), which was attributed to large tilting angles between molecules. By AFM observations, these gels showed well-defined right-handed helical nanofibers formed by coordination bonds in which the helical pitch lengths were strongly dependent on the concentrations of lanthanide ions. In particular, the large luminescence intensity of gel-Tb exhibited a smaller helical pitch length than that of gel-1 due to relatively weak π-π stacking with large tilting angles between molecules. The luminescence intensities were enhanced linearly with increasing concentrations of lanthanide ions. This is the first example of the correlation between the helical pitch length and the luminescence intensity of supramolecular materials. The coordination bonding in supramolecular hydrogels had a strong influence on rheological properties. We also developed a water-compatible inkjet printing system to generate luminescent supramolecular gels on A4-sized paper. The images of a logo and the text were composed of three different emissions and were well-printed on A4 sized paper coated with gel-1.

Ultraviolet Patterned Calixarene-Derived Supramolecular Gels and Films with Spatially Resolved Mechanical and Fluorescent Properties

Supramolecular assemblies have in the past been considered mechanically weak and in most cases unable to withstand their own weight. Calixarene-derived networks can, however, provide robust supramolecular gels. Incorporating a photoreactive stilbene moiety, we show that the aggregation state of the material can be tuned by heating and UV exposure in order to control the mechanical as well as the fluorescent properties. Regulating the extent of heating to control the proportion of H-aggregates and J-aggregates and further cross-linking of H-aggregates by control over UV exposure allows for adjustable photopatterning of the fluorescence as well as the material stiffness in the range from ∼100 to 450 kPa. We expect this straightforward supramolecular system will be suitable for advanced prototyping in applications where modulus and shape are important design criteria.