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In this study, we investigate what types of cellulosic materials are formed by soaking the cellulose/ionic liquid (1-butyl-3-methylimidazolium chloride, BMIMCl) solutions in various organic liquids. When the 5-wt% cellulose/BMIMCl solutions were soaked in organic liquids with high and moderate polarities (relative permittivities), the corresponding cellulosic solutions and gels were produced, respectively. On the other hand, soaking the cellulose/BMIMCl solutions in lower polar liquids resulted in aggregation of cellulose in the mixtures. As the gels with high boiling point media were stable, they were characterized by viscoelastic and compression measurements. Contents of organic media and BMIMCl in the gels were changed depending on the polarities, which affected the mechanical properties under compression mode. Furthermore, processes for production of the solution, gel, and aggregate were proposed.

Herein, we report that chitin hexanoate-graft-poly(ε-caprolactone) (ChHex-g-PCL) is thermoplastic, as confirmed by the formation of a melt-pressed film. Chitin hexanoates with degrees of substitution (DSs) of 1.4-1.8 and bearing free hydroxy groups were first prepared by the hexanoylation of chitin using adjusted feed equivalents of hexanoyl chloride in the presence of pyridine and N,N-dimethyl-4-aminopyridine in 1-allyl-3-methylimidazolium bromide, an ionic liquid. Surface-initiated ring-opening graft polymerization of ε-caprolactone from the hydroxy groups of the chitin hexanoates was conducted in the presence of tin(II) 2-ethylhexanoate as the catalyst at 100 °C to produce (ChHex-g-PCL)s. The feed equivalent of the catalyst, reaction time, and DS value were found to affect the molar substitution and degree of polymerization of the PCL graft chains. Longer PCL graft chains formed their crystalline structures and the (ChHex-g-PCL)s largely contained uncrystallized chitin chains. Accordingly, these (ChHex-g-PCL)s exhibited melting points associated with the PCL graft chains, leading to thermoplasticity.

We previously reported the preparation of a self-assembled chitin nanofiber (ChNF) film via regeneration from an ion gel with an ionic liquid, 1-allyl-3-methylimidazolium bromide using methanol, followed by sonication and filtration. In this study, the resulting ChNF film was cationized by partial deacetylation and subsequent dispersion in aqueous formic acid, which was then employed as a reinforcing agent for composition with xanthan gum. Xanthan gum hydrogels, which were obtained by exchanging disperse media from xanthan gum ion gels with an ionic liquid, 1-butyl-3-methylimidazolium chloride, were soaked in the cationic ChNF aqueous formic acid dispersions with different degrees of deacetylation (DDAs) to progress composition by ion exchange, to fabricate the ChNF-reinforced xanthan gum hydrogels. The presence of ChNFs in the hydrogels was evaluated by SEM measurement of the lyophilized samples from the hydrogels. The amounts of ChNFs in the hydrogels were depending on the DDA values. The compression testing of the hydrogels indicated the reinforcing effect of ChNFs, which were probably induced by electrostatic interaction owing to anionic nature of xanthan gum.

In this study, chitin was nanofibrillated, cationized, and then used as a reinforcing agent for xanthan gum hydrogels. Amidinated chitin nanofibers (CNFs), which were prepared by partial deacetylation of the nanofibrillated chitin and the subsequent reaction of the generated amino groups with N,N-dimethylacetamide dimethyl acetal, were converted into an amidinium chitin bicarbonate with nanofiber morphology by CO2 gas bubbling and ultrasonic treatments in water. Xanthan gum hydrogels, which were prepared by exchange of disperse media from xantham gum ion gels with 1-butyl-3-methylimidazolium chloride, were then soaked in the resulting cationic CNF aqueous dispersions with different degrees of substitution (DSs) of amidinium groups to progress composition, giving rise to the CNF-reinforced xanthan gum hydrogels. The presence of CNFs in the hydrogels was confirmed by SEM measurement of the lyophilized samples. The amounts of CNFs in the hydrogels increased with increasing the DS values. The compression testing of the hydrogels suggested the reinforcing effect of CNFs, which were induced by electrostatic interaction owing to anionic nature of xanthan gum.

Based on our previous work on successful gelation of poly(2-methyl-2-oxazoline)-grafted chitin nanofibers (ChNFs) with high polar media, in this study, we investigated the preparation and gelation behaviors of the ChNFs having different poly(2-alkyl-2-oxazoline) graft chains, that is, poly(2-methyl-2-oxazoline), poly(2-isopropyl-2-oxazoline), and poly(2-butyl-2-oxazoline), with various disperse media. The grafting was carried out by reactions of living propagating ends of poly(2-alkyl-2-oxazoline)s with amino groups present on the self-assembled ChNFs, which were obtained from a chitin ion gel. The products formed gels in the reaction mixtures, which could be converted into hydrogels. All the products with the three poly(2-alkyl-2-oxazoline) graft chains formed gels with high polar media. Besides, gelation of the product with poly(2-butyl-2-oxazoline) was observed by immersing it in relatively non-polar media such as benzyl alcohol, ethyl acetate, and toluene. The formation process of network structures by the grafting of poly(2-alkyl-2-oxazoline)s on ChNFs is proposed to induce gelation of the products.

Based on the fact that an ionic liquid, 1-allyl-3-methylimidazolium bromide (AMIMBr), efficiently dissolved α-chitin, this study investigated the development of facile acylation reactions of α-chitin in AMIMBr media. Under optimal conditions in the presence of pyridine and N,N-dimethyl-4-aminopyridine as base and catalyst, respectively, lauroylation of α-chitin smoothly took place using lauroyl chloride in AMIMBr at 100 °C for 24 h to produce a chitin laurate with a high degree of substitution (DS). Chitin acylates having different substituents were also synthesized by acylation of α-chitin using various acyl chlorides under the same conditions. In addition to IR analysis of the products, 1H NMR measurement was allowed for structure confirmation owing to the dissolution of the high DS derivatives in CDCl3/CF3CO2H mixed solvents.

Double helix formation from the non-natural anionic and cationic amylose analog polysaccharides (amylouronic acid and amylosamine, respectively) was achieved through electrostatic interactions. A water-insoluble complex was obtained by simply mixing the two polysaccharides in water. The 1H NMR analysis indicated that the formation of the complexes with an approximately equimolar unit ratio from the two polysaccharides was resulted regardless of feed ratios for mixing. The powder X-ray diffraction (XRD) measurement suggested that the helix had larger sizes both in diameter and pitch compared with well-known amylose double helix. The formation of the double helical structure was also examined by theoretical calculations. The double helix models, differing in a chain polarity and a charge state of the residues, were constructed based on the 6-fold left-handed amylose chain of the A-amylose crystal structure. Molecular dynamics calculations indicated that those with an antiparallel chain polarity retained an intertwined form. The antiparallel double helical model with the free form residues was suggested to be the most likely structure for the non-natural polysaccharides.

In this study, we investigated the preparation of cationic/anionic chitin nanofiber (CNF) composite materials by electrostatic interaction. An aqueous dispersion of amidinium CNF was prepared by a top-down approach, and a maleylated CNF film was obtained by a bottom-up approach from a chitin ion gel in an ionic liquid with subsequent maleylation on the CNFs. The resulting film was dispersed in ammonia (aq), which was then mixed with the aqueous cationic CNF dispersion to give the composite film. The composition of the two CNFs was evaluated by scanning electron microscopy and X-ray diffraction measurements. Tensile testing results indicated that the mechanical properties of the composites were enhanced with increasing degrees of substitution of the cationic and anionic groups on CNFs, and also when the molar ratio of these groups approached 1:1. The dissociation of the two kinds of CNFs by alkaline treatment of the composite film was achieved, suggesting the presence of an electrostatic interaction among the interactions between them.

Amylose, a natural polysaccharides, is a well-known functional material, because it forms double helix and inclusion complex assemblies depending on whether guest compounds are present or not, owing to its left-handed helical conformation. Amylose is precisely synthesized by phosphorylase-catalyzed enzymatic polymerization. In this study, we investigated the phosphorylase-catalyzed enzymatic polymerization initiated from maltoheptalose (primer for the polymerization)-grafted poly(γ-glutamic acid) in the presence of different feed ratios of a guest polymer, poly(e-caprolactone) (PCL). In the absence of PCL or presence of less amount of PCL, the reaction mixtures totally turned into hydrogel form, predominantly composed of amylose double helixes. On the other hand, aggregates, which were largely composed of amylose inclusion complexes, were formed in the reaction mixtures in the presence of larger amount of PCL. The analytical results indicated that double helix cross-linking points participated into the formation of larger network structure, whereas smaller network structure was fabricated from inclusion complex cross-linking points. These structures on molecular level hierarchically constructed different macroscopic network sizes, leading to difference in the material forms.

This study investigated the fabrication of a nanochitin film via the aggregation of scaled-down chitin nanofibers (SD-ChNFs). A self-assembled ChNF film, which was prepared by regeneration from a chitin/ionic liquid ion gel using methanol, followed by filtration, was treated with aqueous NaOH for deacetylation and subsequently disintegrated by cationization and electrostatic repulsion in 1.0 mol/L aqueous acetic acid with ultrasonication to give a SD-ChNF dispersion. Isolation of the SD-ChNFs via filtration of the dispersion resulted in a highly flexible self-assembled ChNF film that bent and twisted easily. The film exhibited superior mechanical properties compared to the parent self-assembled ChNF film, where the flexibility was further enhanced by the compositing the SD-ChNFs with an anionic polysaccharide, namely ι-carrageenan, via multi-point ionic cross-linking. These enhanced mechanical properties and efficient compositing properties were attributed to the scaling down of the ChNFs.

We have previously reported that re-dispersible amidinium chitin nanofibers are obtained from an amidinated chitin by CO2 gas bubbling with ultrasonic treatment in water. On the other hand, amylose is precisely synthesized by phosphorylase-catalyzed enzymatic polymerization. In this study, grafting of amylose on the amidinium chitin nanofibers was investigated by the phosphorylase-catalyzed enzymatic polymerization to produce amylose-grafted chitin nanofiber materials. Depending on the reaction conditions, the reaction mixtures turned into hydrogels. The hydrogels were constructed via the formation of double helixes from a part of amylose graft chains closely present among the nanofibers. Microstructures, which were hierarchically constructed by lyophilization of the hydrogels, were changed from network to porous morphologies in accordance with the molecular weights of amylose graft chains. Most of the amylose graft chains with higher molecular weights, which did not participate in double helixes, formed amorphous membranes in the nanofiber networks by lyophilization, to construct porous structures.

In this study, we found that a new artificial crystalline structure was fabricated from an amylose analog polysaccharide without hydroxy groups at the C-2 position, i.e., 2-deoxyamylose. The polysaccharide with a well-defined structure was synthesized by facile thermostable α-glucan phosphorylase-catalyzed enzymatic polymerization. Powder X-ray diffraction (XRD) analysis of the product indicated the formation of a specific crystalline structure that was completely different from the well-known double helix of the natural polysaccharide, amylose. Molecular dynamics simulations showed that the isolated chains of 2-deoxyamylose spontaneously assembled to a novel double helix based on building blocks with controlled hydrophobicity arising from pyranose ring stacking. The simulation results corresponded with the XRD patterns.

Amylose, a natural polysaccharide, acts as a host molecule to form supramolecular inclusion complexes in its enzymatically formation process, that is, phosphorylase-catalyzed enzymatic polymerization using the &alpha, d-glucose 1-phosphate monomer and the maltooligosaccharide primer, in the presence of appropriate guest polymers (vine-twining polymerization). Furthermore, in the vine-twining polymerization using maltooligosaccharide primer-grafted polymers, such as maltoheptaose (G7)-grafted poly(&gamma, glutamic acid) (PGA), in the presence of poly(&epsilon, caprolactone) (PCL), the enzymatically elongated amylose graft chains have formed inclusion complexes with PCL among the PGA main-chains to construct supramolecular networks. Either hydrogelation or aggregation as a macroscopic morphology from the products was observed in accordance with PCL/primer feed ratios. In this study, we evaluated macroscopic morphologies from such amylosic supramolecular networks with different guest polymers in the vine-twining polymerization using G7-grafted PGA in the presence of polytetrahydrofuran (PTHF), PCL, and poly(l-lactide) (PLLA). Consequently, we found that the reaction mixture using PTHF totally turned into a hydrogel form, whereas the products using PCL and PLLA were aggregated in the reaction mixtures. The produced networks were characterized by powder X-ray diffraction and scanning electron microscopic measurements. The difference in the macroscopic morphologies was reasonably explained by stabilities of the complexes depending on the guest polymers.

We previously found that the methanol-treatment of a chitin ion gel with an ionic liquid, 1-allyl-3-methylimidazolium bromide, for regeneration and subsequent filtration of a resulting self-assembled chitin nanofiber (CNF) dispersion gave a CNF film. In this study, we investigated a chemoenzymatic approach including enzymatic polymerization catalyzed by phosphorylase for the preparation of amylose-grafted CNF network materials. Maltoheptaose (Glc7) as the primer for the enzymatic polymerization was immobilized on the CNF film by reductive amination with amino groups, generated by the partial deacetylation of chitin molecules. The enzymatic polymerization of α-d-glucose 1-phosphate as a monomer catalyzed by phosphorylase was then conducted from the Glc7 chain ends on the CNFs dispersed in a sodium acetate aqueous buffer. The elongated amylose graft chains spontaneously constructed double helixes for cross-linking among CNFs to produce networks, resulting in a hydrogel. A robust cryogel was obtained by lyop...

In this article, we report the synthesis of a hyperbranched supramolecular polymer composed of continuum of amylose-poly( l -lactide) (PLLA) inclusion complexes by phosphorylase-catalyzed enzymatic polymerization using a branched maltoheptaose-PLLA conjugate according vine-twining polymerization manner. The X-ray diffraction and 1H NMR measurements indicated the presence of the inclusion complex structure in the product. The GPC peak of the amylose segment, which was obtained by alkaline hydrolysis of the vine-twining polymerization product, shifted to the lower molecular weight region, compared with that of the product, supporting the structure of the supramolecular polymer. A hydrogel of the supramolecular polymer was obtained through the formation of an ion gel with an ionic liquid. Furthermore, a cryogel with porous morphology was produced by lyophilization of the hydrogel.

In this study, we investigated the preparation of chitin nanofiber (CNF)-reinforced cellulose films through stepwise regeneration procedures from the respective ion gels with ionic liquids. Self-assembled CNF dispersions were prepared by regeneration from the chitin ion gel with the ionic liquid, 1-allyl-3-methylimidazolium bromide, using methanol, followed by dilution with adjusted amounts of methanol. Cellulose ion gels with the ionic liquid, 1-butyl-3-methylimidazolium chloride, were then prepared, soaked in the CNF dispersions, and centrifuged to simultaneously occur regeneration of cellulose and compatibilization with the CNFs. Soxhlet extraction with methanol and subsequent drying of the resulting materials gave the CNF/cellulose composite films. The IR and SEM results of the films indicated the presence of CNFs not only on the surfaces of the films but also inside the films. Powder X-ray diffraction patterns showed the amorphous structure of the cellulose in the film. Tensile testing of the films suggested the reinforcing effect of the CNFs on the mechanical properties of the films.

In this study, we prepared mutiformable functional supramolecular gels by vine-twining polymerization using poly(γ-glutamic acid-graft-e-caprolactone) (PGA-g-PCL) as a new guest polymer, with subsequent procedures of lyophilization and exchange of dispersion media. When the phosphorylase-catalyzed enzymatic polymerization of the monomer α-D-glucose 1-phosphate from a maltoheptaose primer was carried out in the presence of PGA-g-PCL according to the vine-twining polymerization method, a supramolecular hydrogel was obtained. The resulting hydrogel, purified by soaking in water, had the self-standing properties. Macroscopic interfacial healing was achieved by the formation of inclusion complexes at the interface between two hydrogel pieces through enzymatic polymerization. Cryogels were obtained by the lyophilization of the hydrogels; XRD analysis of the cryogel indicated the presence of inclusion complexes of amylose with PCL graft chains in intermolecular (PGA-g-PCL)s, which acted as cross-linking points for hydrogelation. Porous morphologies were seen in scanning electron micrographs of the cryogels. Furthermore, ion gels were fabricated by soaking the hydrogels in the ionic liquid of 1-butyl-3-methylimidazolium chloride. The mechanical properties of the cryo- and ion gels were evaluated by compressive and tensile testing, respectively.

This paper reports the preparation of chitin nanofiber-graft-poly(2-hydroxyethyl acrylate) (CNF-g-polyHEA) films by surface-initiated atom transfer radical polymerization (ATRP) of HEA monomer from a CNF macroinitiator film. First, a CNF film was prepared by regeneration from a chitin ion gel with an ionic liquid. Then, acylation of the CNF surface with α-bromoisobutyryl bromide was carried out to obtain the CNF macroinitiator film having the initiating moieties (α-bromoisobutyrate group). The surface-initiated graft polymerization of HEA from the CNF macroinitiator film by ATRP was performed to produce the CNF-g-polyHEA film. The IR, XRD, and SEM measurements of the resulting film indicated the progress of the graft polymerization of HEA on surface of CNFs. The molecular weights of the grafted polyHEAs increased with prolonged polymerization times, which affected the mechanical properties of the films under tensile mode.

In this paper, we report acetylation of xanthan gum using acetic anhydride in an ionic liquid solvent, 1-butyl-3-methylimidazolium chloride (BMIMCl). Xanthan gum was dissolved with BMIMCl [2 % (w/w)] and the reaction was carried out in the presence of acetic anhydride (five equiv. for hydroxy groups in a repeating unit) with stirring the solution at elevated temperatures. The structures of xanthan gum acetates were confirmed by the 1H NMR and IR spectra. The degree of acetylation (DA) values determined by the 1H NMR analysis increased with the higher reaction temperatures. The thermal gravimetric analysis (TGA) indicated the enhancement of thermal stability by acetylation. Furthermore, the TGA as well as differential scanning calorimetric (DSC) analysis of the products suggested the presence of the highly and less acetylated segments in a xanthan gum chain. The DSC profile of the product with the high DA value also exhibited a small endothermic peak, which might potentially be ascribed to the melting temperature.

This article reports the enzymatic synthesis of dendritic amphoteric α-glucans having both glucuronic acid and glucosamine residues at the non-reducing ends by thermostable phosphorylase-catalyzed successive glucuronylation and glucosaminylation of a glucan dendrimer having α-(1 → 4)-glucan non-reducing ends using α-D-glucuronic acid 1-phosphate and α-D-glucosamine 1-phosphate as glycosyl donors, respectively. The structure of the products is confirmed by the (1)H NMR analysis. The products exhibit inherent isoelectric points (pIs) determined by the ζ-potential measurement. These materials self-assemble in water at pH = pI to form large aggregates, but disassemble at pH shifted from pI.

This paper reports the preparation of cellulose/xanthan gum composite films and hydrogels through gelation with an ionic liquid. Mixtures of cellulose and xanthan gum in desired weight ratios with an ionic liquid, 1-butyl-3-methylimidazolium chloride (BMIMCl), were thinly placed on a Petri dish and heated at 100 °C for 9 h to obtain the solutions. Then, the solutions were left standing at room temperature for 1 day for the progress of gelation. The resulting ion gels were subjected to Soxhlet extraction with ethanol to remove BMIMCl, followed by drying under ambient conditions to obtain the composite films. The crystalline structures of the polysaccharides and the mechanical properties were evaluated by powder X-ray diffraction measurement and tensile testing of the films, respectively. The ion gels in various cellulose/xanthan gum weight ratios, which were prepared in a test tube by the same procedure, were immersed in water for the exchange of disperse media to obtain the cellulose/xanthan gum composite hydrogels. Water contents of all the materials were higher than 90 %. The mechanical properties of the hydrogels were evaluated by compressive testing.

In the previous study, we successfully prepared a chitin nanofiber film by regeneration from a chitin ion gel with an ionic liquid using methanol. In this study, we performed surface-initiated graft polymerization of γ-benzyl l-glutamate N-carboxyanhydride (BLG-NCA) from amino groups on a partially deacetylated chitin nanofiber (PDA-CNF) film. First, the chitin nanofiber film was immersed in 40 % NaOH aq. at 80 °C for 7 h for partial deacetylation. Then, the PDA-CNF film was immersed in a solution of BLG-NCA in ethyl acetate at 0 °C for 24 h for graft polymerization from amino groups on nanofibers to give a chitin nanofiber-graft-poly(γ-benzyl l-glutamate) (CNF-g-PBLG) film. The analytical results of the film indicated that graft polymerization of BLG-NCA occur on surface of nanofibers. Furthermore, the film was treated with 1.0 mol/L NaOH aq. to convert PBLG on nanofibers into poly(γ-l-glutamic acid sodium salt) (PLGA). Then, condensation of the resulting carboxylates with amino groups at the terminal ends of PLGAs or the remaining amino groups on nanofibers was performed using the condensing agent to produce a CNF-g-PLGA network film. The resulting film showed the good mechanical properties with high flexibility, which has potentials as promising materials for practical applications.

This paper reports the preparation of chitin/cellulose films compatibilized with polymeric ionic liquids. In-situ (co)polymerization of polymerizable ionic liquids, 1-(3-methacryloyloxypropyl)-3-vinylimidazolium bromide (1) and 1-methyl-3-vinylbenzylimidazolium chloride (3), was carried out in the presence of a radical initiator, AIBN, in the chitin/cellulose solution with ionic liquid solvents (1-butyl-3-methylimidazolium acetate and chloride, BMIMOAc and BMIMCl, respectively), followed by the appropriate procedure to give the desired films. The presence of the polymeric ionic liquid in the film was confirmed by the IR measurement. The powder X-ray diffraction analysis suggested that crystalline structures of the polysaccharides were largely disrupted in the film, as same as that of a chitin/cellulose film prepared by the AMIMOAc/BMIMCl system. These results were different from the XRD result of a chitin/cellulose film prepared by the 1-allyl-3-methylimidazolium bromide/BMIMCl system reported in our previous study, in which some crystalline structures were still remained in the film. Furthermore, the mechanical properties of the present films were evaluated by tensile testing, which were affected by the molar ratios of the polymeric ionic liquids to the polysaccharides and the compositional ratios of the two units 1 and 3.

In this paper, we report atom transfer radical polymerization of N -isopropylacrylamide (NIPAAm) by an enzyme mimetic catalyst, that is, hematin of a ferriprotoporphyrin complex. The hematin-catalyzed polymerization of NIPAAm was carried out in the presence of an alkyl halide as an initiator and a reducing agent in DMF/H 2 O solvent. The reaction proceeded at room temperature and the M n s increased with increasing monomer conversions. The M n values were relatively close to the theoretical ones. The reaction did not take place in the absence of any one of the initiator, catalyst, and reducing agent. The 1 H NMR spectrum of the low molecular weight polyNIPAAm indicated the presence of the moieties from the initiator at the polymer ends. These results suggested that the reaction was initiated from radical species, which were produced by bromide abstraction from the initiator by the reduced catalyst.

α-Glucan phosphorylase catalyzes enzymatic polymerization of α- d -glucose 1-phosphate (Glc-1-P) as a monomer from a maltooligosaccharide primer to produce α(1→4)-glucan, i.e., amylose, with liberating inorganic phosphate (Pi). Because of quite weak specificity for the recognition of substrates by thermostable α-glucan phosphorylase (from Aquifex aeolicus VF5), in this study, we investigated the enzymatic copolymerization of Glc-1-P with its analogue monomer, α- d -mannose 1-phosphate (Man-1-P) under the conditions for removal of Pi as the precipitate with ammonium and magnesium in ammonia buffer containing Mg2+ ion to produce α(1→4)-linked non-natural mannoglucans composed of Glc/Man units. The reaction was conducted in different feed ratios using the maltotriose primer at 40 °C for 7 days. The MALDI-TOF mass and 1H NMR spectra of the products fully supported the mannoglucan structures.

This paper reports the preparation of chitin nanofiber-graft-poly( l -lactide-co-e-caprolactone) films by surface-initiated ring-opening graft copolymerization of l -lactide (LA)/e-caprolactone (CL) monomers from chitin nanofiber films. First, the chitin nanofiber film was prepared according to our previous method. Then, the film was immersed in water and lyophilized for pre-treatment. The non-treated or pre-treated film was immersed in a solution of LA/CL in toluene for 12 h. After tin(II)-2-ethylhexanoate as a polymerization catalyst was added to the mixture, which was heated at 80 °C for 48 h for the progress of copolymerization, the resulting film was washed and further subjected to Soxhlet extraction with chloroform. The IR spectrum of the obtained film exhibited carbonyl absorption at 1739 cm−1 due to the ester linkage of poly(LA-co-CL), suggesting the presence of poly(LA-co-CL). The powder X-ray diffraction and SEM measurements of the obtained film indicated that the graft copolymerization of LA/CL was initiated from hydroxy groups on surface of the chitin nanofibers. The mechanical properties of the films, which were evaluated by tensile testing, were affected by the amounts and the LA/CL composition ratios of the grafted polyesters.

Poly(spiropyran)s were synthesized by polycondensation of a bis(indoline) monomer with bis( o -positioned formyl and hydroxy)-substituted aromatic monomers in alcoholic solvents. The structures of the products and their molecular weights were determined by the 1 H NMR and GPC measurements, respectively. Furthermore, photoisomerization behaviors of the poly(spiropyran)s were analyzed by the UV–Vis and 1 H NMR measurements of their solutions in dichloromethane upon the UV and visible light irradiations.

Imogolite is one of the clay minerals contained in volcanic ash soils. The novel hybrid hydrogels were prepared from imogolite nanofibers and DNA by utilizing strong interaction between the aluminol groups on imogolite surface and phosphate groups of DNA. The hybrid hydrogels of imogolite and DNA were prepared in various feed ratios, and their physicochemical properties and molecular aggregation states were investigated in both dispersion and gel states. The maximum DNA content in the hybrid gels was shown in equivalent molar ratio of imogolite and DNA. The physical properties of the hybrid gels were changed by varying DNA blend ratios. In the dispersion state, the hybrid gels showed a fibrous structure of imogolite, whereas a continuous network structure was observed in pure imogolite, indicating that the hybrid with DNA enhanced the dispersion of imogolite. In the gel state, DNA and imogolite nanofibers formed a 3D network structure.

In this study, we performed the facile preparation of chitin/cellulose composite films using two ionic liquids, 1-allyl-3-methylimidazolium bromide (AMIMBr) and 1-butyl-3-methylimidazolium chloride (BMIMCl); the former dissolves chitin and the latter dissolves cellulose. First, solutions of chitin in AMIMBr and cellulose in BMIMCl were individually prepared by heating each mixture at 100 °C for 24 h. Then, the homogeneous mixture of the two solutions was thinly casted on a glass plate, followed by standing at room temperature for 2 h. After the material was subjected to successive Soxhlet extractions with ethanol for 12 h and with water for 12 h, the residue was dried at room temperature to give a composite film. The crystalline structures of the polysaccharides were evaluated by the X-ray diffraction measurement. Furthermore, the thermal stability and mechanical property of the resulting composite film were estimated by the thermal gravimetric analysis measurement and tensile testing, respectively.

Our previous research showed that a simple ultra-high-pressure process made poly(vinyl alcohol) (PVA) solution into a macrogel and nanoparticles. To investigate the release properties of PVA hydrogels prepared by the ultra-high-pressure treatment, we prepared hydrogels containing model drugs by pressurizing a PVA solution with Alfa-G Hesperidin or Oil Blue N as a water-soluble or an oil-soluble model drug, respectively. In the case of the oil-soluble drug, an oil-in-water emulsion, Oil Blue N containing dodecane in a PVA solution, was used by homogenization before pressurization. The average diameter and the diameter distribution of oil droplets before and after the ultra-high-pressure treatment were almost the same. However, the PVA hydrogel prepared at 10,000 atm for 10 min exhibited the slowest release rate of model drugs. Thus, we found that the release rates of the model drugs from the PVA hydrogels were controlled by the degree of crosslinking in the resulting gels, which was determined from the operation parameters of the ultra-high-pressure treatment, such as the pressure, time, and concentration of the PVA solution. Therefore, an ultra-high-pressure process is promising for drug-carrier development because of the nonharmful simple preparation process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

We report here a reversible self-assembly formation system using block copolymers with thermo-tunable properties. A series of double-responsive block copolymers, poly(N-isopropylacrylamide (NIPAAm))-block-poly(NIPAAm-co-N-(isobutoxymethyl)acrylamide (BMAAm)) with two lower critical solution temperatures were synthesized by one-pot atom transfer radical polymerization via sequential monomer addition. When dissolved in aqueous solution at room temperature, the block copolymers remained unimeric. Upon heating above room temperature, the block copolymers self-assembled into micellar structures. The micelle formation temperature and the resulting diameter were controlled by varying the BMAAm content. 1H Nuclear Magnetic Resonance, dynamic light scattering, field-emission scanning electron microscopy, and fluorescence spectra revealed the presence of a monodisperse nanoassembly, and demonstrated the assembly formation/inversion process was fully reversible. Moreover, a model hydrophobic molecule, pyrene, was successfully loaded into the micelle core by including pyrene in the original polymer solution. Further heating resulted in mesoscopic micelle aggregation and precipitation. This dual micelle and aggregation system will find utility in drug delivery applications as a thermal trigger permits both aqueous loading of hydrophobic drugs and their subsequent release. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

In this study, we prepared cross-linked aliphatic polyester derived from branched poly(ɛ-caprolactone (abbreviated as CL)- co - d , l -lactide (abbreviated as LA)) macromonomers with different CL and LA compositions and investigated the effect of thermal properties on their degradation. According to the degradation study, the weight loss became larger with increasing LA composition in poly(CL- co -LA). The introduction of LA units that can degrade easily disturbed the crystallinity of the PCL segments; as result, the hydrolysis became accelerated. Also, we studied the temperature dependency of degradation of a series of cross-linked poly(CL- co -LA) materials with different melting points. We found that the degradation of these materials related closely to the crystallinity, which could be controlled by the composition of CL and LA.

Coil-Globule Transition and/or Coacervation of Temperature and pH Dual-Responsive Carboxylated Poly( N -isopropylacrylamide)

In this thesis, we studied the convenient synthesis and characterizations of thermo-responsive materials with double response. To achieve these, AB-type diblock copolymers comprising of poly(N-isopropylacrylamide) (NIPAAm) segment and poly(NIPAAm-co-(N-(hydroxymethyl)acrylamide) (HMAAm)) one were designed. That was synthesized in one-pot using an atom transfer radical polymerization (ATRP) technique. Poly(NIPAAm-co-HMAAm)s synthesized separately showed sensitive thermo-response and the cloud point was completely tunable by the composition of HMAAm. As expected, the block copolymers exhibited double thermo-responsive profiles in aqueous solution. The responsive behavior was discussed by precise trace by 1H NMR and turbidity measurements. From these results, we could confirm almost independent dehydration of each segment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6142–6150, 2008

Preparation, Characterization and Biocompatibility Study of the Scaffold Prototype Derived from Cross-Linked Poly[(e-caprolactone)- co -lactide] for Tissue Engineering Materials

Controlling the noncovalent bondings such as electrostatic interaction, van der Waals force and hydrogen bond, is the key factor to generate molecular assembly. We show that pressure is one of the most intensive variables for controlling these intermolecular forces and producing assembled structure. Macrogel and nanoparticles of hydrogen-bonded polymers were simply obtained through an ultrahigh-pressure process. The morphology of the obtained assembly depends on concentration and various conditions of the pressurization. These results indicate that the ultrahigh-pressure induces inter/intra-hydrogen bond, which is strong enough to maintain microassemblies such as gels and particles. This methodology leads to the molecular design of pressure-induced molecular assembly, and nonharmful processes for molecular separation and drug development. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 743–750, 2008

The effects of the aspect ratio of multi-walled carbon nanotubes (MWNTs) on the rheology and flammability of polystyrene/MWNT nanocomposites are studied using two MWNTs having average aspect ratios (length to outer diameter) of 49 and 150. Dynamic rheological experiments show that the particles with the larger aspect ratio impart much higher storage moduli and complex viscosities to the nanocomposites compared to equivalent mass loadings of particles with the smaller aspect ratio. Additionally, in flammability experiments, the larger aspect ratio particles lead to a greater reduction in mass loss rate, i.e., they are more effective at reducing flammability. These results demonstrate that the aspect ratio of MWNTs is a key parameter in controlling the rheology and flammability of polymer nanocomposites.

Particle spatial dispersion is a crucial characteristic of polymer composite materials and this property is recognized as especially important in nanocomposite materials due to the general tendency of nanoparticles to aggregate under processing conditions. We introduce dispersion metrics along with a specified dispersion scale over which material homogeneity is measured and consider how the dispersion metrics correlate quantitatively with the variation of basic nanocomposite properties. We then address the general problem of quantifying nanoparticle spatial dispersion in model nanocomposites of single-walled carbon nanotubes (SWNTs) dispersed in poly(methyl methacrylate) (PMMA) at a fixed SWNT concentration of 0.5% using a ‘coagulation’ fabrication method. Two methods are utilized to measure dispersion, UV–vis spectroscopy and optical confocal microscopy. Quantitative spatial dispersion levels were obtained through image analysis to obtain a ‘relative dispersion index’ (RDI) representing the uniformity of the dispersion of SWNTs in the samples and through absorbance. We find that the storage modulus, electrical conductivity, and flammability property of the nanocomposites correlate well with the RDI. For the nanocomposites containing the same amount of SWNTs, the relationships between the quantified dispersion levels and physical properties show about four orders of magnitude variation in storage modulus, almost eight orders of magnitude variation in electric conductivity, and about 70% reduction in peak mass loss rate at the highest dispersion level used in this study. The observation of such a profound effect of SWNT dispersion indicates the need for objective dispersion metrics for correlating and understanding how the properties of nanocomposites are determined by the concentration, shape and size of the nanotubes.

In this study, cross-linked materials were prepared using the branched macromonomer with different CL/LA molar ratios, and feasibility studies for tissue engineering were carried out. The thermal and mechanical properties of these materials depended on the CL/LA compositions; however, there was no change in the wettability of each material. The HeLa cells adhesion and growth on the CL-LA7030c were equal to that on the commercially available polystyrene dish. The protein absorption experiment using the FBS proteins revealed that the materials with well-grown cells showed better adhesion of the proteins. [photo: see text]

Thermostable α-glucan phosphorylase-catalyzed enzymatic copolymerization of α-d-glucose 1-phosphate (Glc-1-P) with its analogue monomer, α-d-glucosamine 1-phosphate (GlcN-1-P), from a maltotriose primer was performed to produce non-natural heteroaminopolysaccharides composed of Glc/GlcN units, that is, α(1→4)-linked glucosaminoglucans. The GlcN units in the products were further converted to N-acetyl-d-glucosamine (GlcNAc) units by N-acetylation. The structures of the products were evaluated by the MALDI-TOF MS, (1)H NMR, and (1)H-(1)H COSY NMR measurements, which were completely different from those of the natural glycosaminoglycans. The degrees of polymerization and Glc/GlcN compositional ratios of the products were relatively dependent on the Glc-1-P/Glc-1-P/Glc3 feed ratios. The noncrystalline natures of the present materials were supported by the X-ray diffraction measurement.

Polymer hybrids designed on a nanometer scale were prepared by several methods with an aluminosilicate nanofiber, “imogolite.” This review paper introduces the preparation of polymer hybrid materials from imogolite nanofiber by two different approaches. In order to realize the fine dispersion of imogolite in polymer matrix, poly(vinyl alcohol)/imogolite hybrids were prepared by in situ synthesis method of imogolite in polymer solution. In addition, through utilizing the strong interaction between phosphoric acid group and Al–OH on the surface of imogolite, poly(methyl methacrylate)/imogolite hybrid, and enzyme/imogolite hybrid gel were prepared and characterized.

The adsorption of proteins on poly(2-hydroxyethyl methacrylate) (PHEMA) brushes was systematically studied by quartz crystal microbalance (QCM) and fluorescence microscopy as a function of graft density and protein size. The graft density σ (chains/nm2) ranged from 0.007 (dilute or semidilute brush regime) to 0.7 (concentrated brush regime), and the protein size ranged from 2 to 13 nm in an effective diameter. The lowest-density brush (σ = 0.007) adsorbed all the tested four proteins, while the highest-density brush (σ = 0.7) adsorbed none of them. The middle-density brush (σ = 0.06) showed an intermediate behavior, adsorbing the smallest two proteins but effectively repelling the largest two. PHEMA cast films adsorbed a probe protein with the adsorbed amount increasing approximately proportionally to the film thickness, indicating that the adsorption mainly occurred in the bulk of the film. The noted results for the brushes support the idea of size-exclusion effect, an effect characteristic of concentrat...