Ishii Daisuke

Résumé/Abstract Native celluloses from different origins show variant solubility in lithium chloride/amide solvent system. The solubility of some of native cellulose is enhanced by solvent exchange procedure, namely sequential immersion in water, acetone, and amide ...

ABSTRACT Phase transition, orientation under shear and relaxation behavior of thermotropic main-chain liquid crystalline polyesters (LCP) synthesized from ω-[4-(4-hydroxyphenyl)phenoxy]alkyl alcohols with different alkyl unit length and terephthalic or isophthalic acid were investigated. Formation of liquid crystalline phase at the elevated temperatures was observed for the polyesters containing methylene sequences with more than 4 methylene units. Odd-even effect of the number of methylene units on the phase transition temperatures of LCP was observed. Furthermore, terephthalic and isophtalic LCPs showed different phase transition behaviors. These results show that the molecular conformation, determined by the number of methylene units and substitution pattern in aromatic rings, affects the phase transition of LCPs. Molecular orientation under shear and the relaxation behavior was investigated by in situ WAXS experiments.

Dynamic viscoelasticity measurements were performed for aqueous dispersions of cellulose nanofibers prepared by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation and subsequent mechanical disintegration in water. The frequency dependence of the storage and loss moduli of 0.02% (w/v) dispersions of TEMPO-oxidized cellulose nanofibers in water showed terminal relaxation behavior at relatively lower angular frequencies. This strongly suggests that each cellulose nanofiber in the dispersion behaves as a semiflexible rod-like macromolecular chain or colloidal particle. Furthermore, a clear boundary was observed between the terminal relaxation and rubbery plateau regions. The longest viscoelastic relaxation time, τ, was estimated from the angular frequency, corresponding to the boundary point, and the average length of the cellulose nanofibers, L, was estimated using the equation τ = πη(s)L(3)/[18k(B)T ln(L/d)]. The equation gave a value of L = 2.2 μm, which was in good agreement with TEM observations.

We investigated the effect of solvent exchange on the supramolecular structure and the molecular mobility of the cellulose molecule to clarify the mechanism of the dissolution of cellulose in lithium chloride/N,N-dimethylacetamide (LiCl/DMAc). Among the celluloses that were solvent exchanged in different ways, the DMAc-treated celluloses dissolved most rapidly. Dissolution of the acetone-treated celluloses was much slower than the DMAc-treated ones, but considerably faster than the untreated one. Such differences in the dissolution behavior were well explained by the differences in the surface fractal dimension calculated from the small-angle X-ray scattering profiles and in the (1)H spin-lattice and spin-spin relaxation times estimated from the solid-state NMR spectroscopic measurements. Furthermore, it was suggested from the IR spectra and the (13)C spin-lattice relaxation times of cellulose that DMAc is adsorbed on the surface of cellulose even after vacuum-drying and affects the molecular mobility and hydrogen-bonding state of cellulose.

Biocompatibility of PLLA and stereocomplexed PLA nanofibers was evaluated by subcutaneous implantation in rats for 4-12 weeks. Characterization of the nanofibers was performed by GPC, SEM, wide-angle X-ray diffraction, and optical microscopy of hematoxylin-eosin stained ultrathin sections of explanted nanofibers. Stereocomplexed PLA nanofiber showed slower degradation than PLLA nanofiber and thus retained their shape after prolonged implantation. Furthermore, stereocomplexed PLA nanofiber caused milder inflammatory reaction than PLLA nanofiber. These results offer the potential use of PLLA and stereocomplexed PLA nanofibers as a biomaterial for short-term and long-term tissue regeneration, respectively. Stereocomplexed PLA nanofiber after in vitro degradation showed smaller degree of swelling than PLLA nanofiber. Taking the results of in vivo degradation together with in vitro degradation into consideration, bioabsorption mechanism of the in vivo degradation of the nanofibers is proposed.