Chiral-Linkage-Induced Hierarchical Ordering of Colloidal Achiral Nanotubes in their Thixotropic Gel.

Macroscopic continuous hierarchical ordering of achiral nanotube "imogolite" was achieved by thixotropic gelation of imogolite with chiral hydroxy acid and their flow-orienting/subsequent standing for uniaxial alignments of imogolite. The chirality change of the hydroxy acids resulted in an inversion of the helical ordering. The study presented here first exhibits the millimeter-scale supramolecular chirality induced by angstrom-scale molecular handedness in the architecture of nanotubes.

Helical alignment inversion of microtubules in accordance with a structural change in their lattice.

Giant helical (oriented chiral nematic) alignments of microtubules of nanometer to centimeter lengths are known to form over a temperature gradient during anisotropic spiral propagation via tubulin dimer addition in a capillary cell. Such helical alignments may be modified by the addition of either paclitaxel or dimethyl sulfoxide, which induces a lattice (helical) structural change in the microtubule itself. In this study, we found that the lattice structural change of microtubules brings about inversion of microtubule alignments in the helical ordering. Based on microscopy and scattering data, a mechanism for the helical ordering of microtubules is discussed in relation to their lattice (helical) structure.

Direct evidence for structural transition promoting shear thinning in cylindrical colloid assemblies.

In this paper, we describe stimuli-responsive hydrogels prepared from a rigid rod-like polyelectrolyte 'imogolite' and a dicarboxylic acid. The hydrogel exhibited thixotropy in response to mechanical shock within the order of seconds or sub-seconds. Here, using the latest structural/rheological characterisation techniques, the relationship between the structural transition processes and the shear thinning was estimated. The evidence obtained by the experiments revealed for the first time the direct relationship between the microscopic structural change and the macroscopic thixotropic behavior that have been extensively discussed. The thixotropic hydrogel has the hierarchical architecture in the combination of imogolite and dicarboxylic acid, i.e., sheathed nanotubes/hydroclusters of cross-bridged nanotubes/frameworks. The formation and disintegration of the network structure upon resting and agitating, respectively, were the origin of gel/sol transition (thixotropy), although the hydroclusters of cross-bridged nanotubes were maintained throughout the transition.

Thermoresponsive synthetic polymer-microtubule hybrids.

Thermoresponsive hybrids consisting of synthetic polymers and microtubules (MTs), i.e., assemblies of tubulins, were prepared by bonding MTs covalently to a few reactive units in a macromolecular strand. The hybrids exhibited the gel/sol transition because of the "assembling of tubulins to MTs/disintegrating of MTs to tubulins" by the temperature change between 37 and 4 °C, respectively. The viscoelastic behaviors of the hybrid gels depended upon the quantity of polymer feed and the amount of resulting covalent bonds between the polymers and tubulin units. Furthermore, in a confined space of a thin and long rectangular cell with the temperature gradient from 4 °C (cold terminal) to 37 °C (warm terminal), the sol state hybrid turned to the gel state that propagated from the warm terminal toward the cold terminal to form uniaxially oriented MT arrays. Upon changing the temperature of the whole system between 37 and 4 °C, the uniaxial arrays appeared/disappeared reversibly.

Structural requirements for producing solvent-free room temperature liquid fullerenes.

A new class of solvent-free room temperature liquid fullerenes was synthesized by attaching a single substituent of 1,3,5-tris(alkyloxy)benzene unit to C60 or C70 under the Prato conditions. Although the C60 monoadducts were single components after chromatographic purification, the C70 monoadducts were isomeric mixtures due to the prolate spheroidal π-chromophore. The alkyl chain length of the substituents significantly affected both melting points and rheological behavior of the fullerene derivatives. When the alkyl chains were short, the intermolecular π-π interactions of adjacent fullerene cores led to a melting point higher than room temperature. In contrast, in the case of exceedingly long alkyl chains, such as eicosyl (-C20H41) and docosanyl (-C22H45) groups, the van der Waals interactions among neighboring alkyl chains became dominant. Accordingly, only medium alkyl chain lengths could provide solvent-free fluidic fullerenes with low melting points. The rheological measurements of the liquid fullerenes at 25 °C revealed their unique liquid characteristics; molecular-level friction (or viscosity) and nanometer-scale clustering were noticed. It is generally thought that alkyl chains serve as a stabilizer of the fullerene core units. Thus, a longer chain or higher plasticity of the stabilizers would promote the disturbance of the core-core interactions. It was indeed shown that longer alkyl chains resulted in a lower fluid viscosity. It was also found that metastable solid phases were produced by the noticeable van der Waals interaction between the long alkyl chains especially when a symmetric C60 core was adopted. This interesting finding enabled the comparison of electrochemical activities of the C60 unit between the solvent-free liquid and metastable solid form, which revealed a superior electrochemical activity in the liquid state.

Structural and mechanical properties of Laponite-PEG hybrid films.

Inorganic/organic hybrids were obtained by the sol-gel type organic modification reaction of Laponite sidewalls with poly(ethylene glycol) (PEG) bearing alkoxysiloxy terminal functionality. By casting an aqueous dispersion of the hybrid, the flexible and transparent hybrid films were obtained. Regardless of the inorganic/organic component ratio, the hybrid film had the ordered structure of Laponite in-plane flat arrays. The mechanical strength of hybrid films was drastically improved by the presence of cross-linking among alkoxysilyl functionalities of PEG terminals and the absence of PEG crystallines. Hybrid films, especially those that consisted of PEG with short chain, showed good mechanical properties that originate from quasi-homogeneous dispersion of components due to anchoring of PEG terminal to Laponite sidewall and interaction of PEG to Laponite surface.

Flexible, transparent nanocomposite film with a large clay component and ordered structure obtained by a simple solution-casting method.

A flexible, transparent nanocomposite (NC) film with 57 wt % inorganic components was obtained by the simple casting of a solution of Laponite and modified organic molecules through a sol-gel reaction. The NC film has solvent resistance and a disco-nematic liquid-crystalline-like structure of Laponite that originates from the cross linking of Laponite by silanol agents and the large amount of Laponite in the film.

Microbial conversion of glucose to a novel chemical building block, 2-pyrone-4,6-dicarboxylic acid.

2-Pyrone-4,6-dicarboxylic acid (PDC) is a catabolic intermediate in Sphingobium sp. SYK-6 (previously characterized as Sphingomonas paucimobilis SYK-6), which is a degrader of lignin-derived aromatic compounds. Recently, PDC has been also characterized as a novel starting material for several potentially useful synthetic polymers. In a previous study, we constructed a biosynthetic system in which PDC was generated efficiently from a chemically synthesized compound, protocatechuate. In order to develop an alternative system for production of PDC, we tried to generate it from glucose, which is a low-cost sugar that can be obtained from abundant cellulosic wastes and biomass crops. We designed a metabolic bypass to PDC from the shikimate pathway in recombinant Escherichia coli cells. PDC accumulated in the medium of recombinant E. coli cells that had been transformed with genes isolated from Emericella niger, E. coli, Pseudomonas putida, and Sphingobium sp. SYK-6. The yield of PDC depended on the combination of genes that we introduced into the cells and on the specific of host strain. Under optimal conditions, the yield and titer of PDC were, respectively, 17.3% and 0.35 mg/l when the concentration of glucose was 2 g/l and the culture volume was 50 ml. Our results open up the possibility of novel utilization of biomass as the source of a useful chemical building block.

Efficient production of 2-pyrone 4,6-dicarboxylic acid as a novel polymer-based material from protocatechuate by microbial function.

Sphingomonas paucimobilis SYK-6, which can degrade various low molecular weight compounds derived from plant polyphenols such as lignin, lignan, and tannin, metabolizes these substances via 2-pyrone-4,6-dicarboxylic acid (PDC). We focused on this metabolic intermediate as a potential raw material for novel, bio-based polymers. We cloned the ligAB and ligC genes of SYK-6, which respectively encode protocatechuate 4,5-dioxygenase and 4-carboxy-2-hydroxymuconate-6-semialdehyde dehydrogenase, into a broad host range plasmid vector, pKT230MC. The resulting plasmid, pDVABC, was introduced into the PpY1100 strain of Pseudomonas putida, and we found that PDC could be stably produced from protocatechuate and accumulated. In addition, we examined the efficiency of production of PDC from protocatechuate on a 5-L scale in a Luria-Bertani medium containing 100 mM glucose and determined that PDC was stably produced from protocatechuate to yield 10 g/L or more.