Preparation and characterization of an imogolite/chitosan hybrid with pyridoxal-5'-phosphate as an interfacial modifier.

Imogolite/chitosan hybrid films were prepared using pyridoxal-5'-phosphate (PLP) as an interfacial modifier. Thermogravimetric analysis and spectroscopic measurements revealed that the phosphate group of PLP was adsorbed on the imogolite. Furthermore, rheological measurements suggested that the PLP-modified imogolites (PLP-imogolite) had strong interactions with chitosan in solution. Moreover, UV absorption of the hybrid film showed that PLP and chitosan formed Schiff base linkages. Therefore, the hybrid films exhibited a significant improvement in their mechanical properties compared to those of pristine chitosan/imogolite hybrid films.

Preparation of an (inorganic/organic) hybrid hydrogel from a peptide oligomer and a tubular aluminosilicate nanofiber.

'Imogolite', a tubular inorganic nanotube surface, was modified with a peptide oligomer to prepare a hybrid hydrogel. The formation of the gels was confirmed by conducting a vial inversion test and rheological measurements. The surface modification of imogolite with the peptide oligomer was verified by performing thermogravimetric analysis and circular dichroism measurements. Furthermore, the formation of the network-like morphology of the prepared hydrogel was confirmed by scanning force microscopy.

Structure and Properties of Hybrid Film Fabricated by Spin-Assisted Layer-by-Layer Assembly of Sacran and Imogolite Nanotubes.

A free-standing (biomacomolecule/synthetic inorganic nanotubes) hybrid film was fabricated through an alternative layer-by-layer (LBL) assembly of sacran and imogolite nanotubes. Sacran is a natural polysaccharide extracted from the cyanobacterium Aphanothece sacrum, while imogolite is a natural tubular aluminosilicate clay found in volcano ash. The hybrid film thickness increased linearly with the number of the bilayers, because of the interaction between the negatively charged surface of sacran and the positively charged surface of imogolite. UV-vis spectroscopy indicated that the LBL film exhibited good transparency. The surface morphology of the LBL film was smooth in the micrometer scale; many imogolite nanotubes were adsorbed onto the sacran layer, while no imogolite clusters were observed. Furthermore, the structure, stability, gas permeability, and mechanical properties of the LBL films were investigated.

Organic-Inorganic Hybrid Films Fabricated from Cellulose Fibers and Imogolite Nanotubes.

Owing to the increasing environmental awareness, nanocellulose/natural clay composites with improved mechanical performance have attracted growing interest due to their eco-friendly properties. In this study, hybrid films composed of cellulose fibers (CFs) and imogolite nanotubes (natural aluminosilicate nanotubes) were fabricated. We mainly studied the structure, density, and properties of the hybrid materials. Specifically, the hybrid materials were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), a rheological test, and wide-angle X-ray diffraction (WAXD). The mechanical properties of the hybrid materials were measured by a tensile test, which demonstrated that the mechanical properties of the hybrid films were considerably improved by the addition of imogolite up to 1 wt %; meanwhile, the thermal-mechanical properties of the hybrid film were also enhanced.

Ionic liquid induces flexibility and thermoplasticity in cellulose film.

It is still challenging to melt-process cellulose. In this paper, we proposed a method for the formation of thermally processable flexible cellulose films via gelation from its solution in ionic liquid (1-butyl-3-methylimidazolium chloride; BMIMCl). Cotton, as a source of cellulose, was dissolved (5 wt%) in BMIMCl and subsequently placed in different amounts of water. The obtained ion gels were dried at 60 °C for 24 h; during drying process, water was removed while BMIMCl was retained. It was found that the amount of retained BMIMCl had a critical role in determining the mechanical properties of the films. It was suspected that the processing conditions altered the degree of crystallinity of cellulose in the films as evidenced by X-ray diffraction measurement. The ionic liquid, i.e., BMIMCl induced the plasticity into the films, so that thermal processability to different shapes became possible.

Effects of self-reported calorie restriction on correlations between SIRT1 polymorphisms and body mass index and long-term weight change.

SIRT1 acts as a cellular sensor to detect energy availability and modulates fat and glucose metabolism. This study assessed the effects of self-reported calorie restriction (CR) and exercise on correlations between SIRT1 polymorphisms and body mass index (BMI) and long-term weight change. This cross-sectional study enrolled 4023 subjects aged 35-69years (1847 men and 2176 women) selected from participants in the Japan Multi-Institutional Collaborative Cohort Study. This study was based on a self-administered questionnaire. No significant correlations between SIRT1 polymorphisms and BMI or long-term weight change were found in either the CR or the active groups. In the no-CR group, women with the rs1467568 G allele had a higher BMI than women without (p=0.02). Moreover, women with the rs7895833 A or rs1467568 G allele gained more weight from the age of 20years than women without these alleles (p=0.03 for rs7895833 and p=0.003 for rs1467568). In addition, the odds ratios (95% confidence intervals) of these alleles for overweight (BMI >27.5kg/m2) were significantly high in the no-CR women group (1.78 (1.06-2.99) for rs7895833 and 1.88 (1.13-3.15) for rs1467568) but not in the CR group. The results of this study suggest that CR might override the genetic contributions of the SIRT1 rs7895833 A and rs1467568 G alleles to BMI and long-term weight change.

Validity of a food frequency questionnaire in a population with high alcohol consumption in Japan.

BACKGROUND AND OBJECTIVES: Alcohol consumption has a relatively large impact on energy intake in drinkers, and several studies reported different dietary habits from non-drinkers. However, few studies have investigated the influence of alcohol consumption on the validity of the Food Frequency Questionnaire (FFQ). To investigate its influence, we conducted a validity test in a population with high alcohol consumption. METHODS AND STUDY DESIGN: The study subjects were 66 residents living on an island in the south-western part of Japan. We conducted the FFQ and 12-day-weighed dietary records (12d-WDRs) in each 3 day of each 4 season. We calculated Pearson correlation coefficients (CCs) and agreement rates according to quartile classification after adjusting for energy. RESULTS: The intake energy (kcal) estimated from 12d-WDRs and FFQ was 1,641 and 1,534 in women, and 2,093 and 1,979 in men, respectively. The cumulative percentage contribution of the alcohol energy was 6.7% in men. De-attenuated, log-transformed Pearson's median CCs between the nutrients quantified with the 12d-WDRs and FFQ were 0.51 in women and 0.38 in men. The CCs for carbohydrate and saturated fatty acids intake of men were lower than those in the previous Tokai study using the same FFQ. The findings in agreement rates were consistent with the Tokai study. CONCLUSION: This study suggested that the FFQ can be used for epidemiological studies using categorical comparisons in this population, although the underestimation of carbohydrates and other nutrients in the FFQ should be taken into consideration.

Intracellular periodontal pathogen exploits recycling pathway to exit from infected cells.

Although human gingival epithelium prevents intrusions by periodontal bacteria, Porphyromonas gingivalis, the most well-known periodontal pathogen, is able to invade gingival epithelial cells and pass through the epithelial barrier into deeper tissues. We previously reported that intracellular P. gingivalis exits from gingival epithelial cells via a recycling pathway. However, the underlying molecular process remains unknown. In the present study, we found that the pathogen localized in early endosomes recruits VAMP2 and Rab4A. VAMP2 was found to be specifically localized in early endosomes, although its localization remained unclear in mammalian cells. A single transmembrane domain of VAMP2 was found to be necessary and sufficient for localizing in early endosomes containing P. gingivalis in gingival epithelial cells. VAMP2 forms a complex with EXOC2/Sec5 and EXOC3/Sec6, whereas Rab4A mediates dissociation of the EXOC complex followed by recruitment of RUFY1/Rabip4, Rab4A effector, and Rab14. Depletion of VAMP2 or Rab4A resulted in accumulation of bacteria in early endosomes and disturbed bacterial exit from infected cells. It is suggested that these novel dynamics allow P. gingivalis to exploit fast recycling pathways promoting further bacterial penetration of gingival tissues.

Antibacterial Activity of Curcumin Against Periodontopathic Bacteria.

BACKGROUND: Curcumin is a polyphenol extracted from root of turmeric and known to possess multifunctional properties, including antibacterial activity. Although previous studies have investigated the effects of curcumin on microorganisms, available knowledge on the effects of curcumin on periodontopathic bacteria is still limited. In this study, the antibacterial effect of curcumin on periodontopathic bacteria is investigated, particularly Porphyromonas gingivalis. METHODS: Representative periodontopathic bacteria were cultured in media with and without various curcumin concentrations, and the optical density at 600 nm was measured for 60 hours. The inhibitory effect of curcumin on P. gingivalis Arg- and Lys-specific proteinase (RGP and KGP, respectively) activities were assessed using spectrofluorophotometric assay. Analysis of biofilm formation by P. gingivalis with or without Streptococcus gordonii was conducted using confocal laser-scanning microscopy (CLSM). RESULTS: Curcumin inhibited the growth of P. gingivalis, Prevotella intermedia, Fusobacterium nucleatum, and Treponema denticola in a dose-dependent manner. Bacterial growth was suppressed almost completely at very low concentrations of curcumin. Conversely, 100 µg/mL curcumin did not suppress the growth of Aggregatibacter actinomycetemcomitans. It also demonstrated inhibitory effects against RGP and KGP activities in a dose-dependent manner. CLSM revealed that curcumin suppressed P. gingivalis homotypic and P. gingivalis-S. gordonii heterotypic biofilm formation in a dose-dependent manner. A concentration of 20 µg/mL curcumin inhibited these P. gingivalis biofilm formations by >80%. CONCLUSION: Curcumin possesses antibacterial activity against periodontopathic bacteria and may be a potent agent for preventing periodontal diseases.

Fabrication and characterization of polysaccharide ion gels with ionic liquids and their further conversion into value-added sustainable materials.

A review of the fabrication of polysaccharide ion gels with ionic liquids is presented. From various polysaccharides, the corresponding ion gels were fabricated through the dissolution with ionic liquids. As ionic liquids, in the most cases, 1-butyl-3-methylimidazolium chloride has been used, whereas 1-allyl-3methylimidazolium acetate was specifically used for chitin. The resulting ion gels have been characterized by suitable analytical measurements. Characterization of a pregel state by viscoelastic measurement provided the molecular weight information. Furthermore, the polysaccharide ion gels have been converted into value-added sustainable materials by appropriate procedures, such as exchange with other disperse media and regeneration.

Stereochemistry-dependent, mechanoresponsive supramolecular host assemblies for fullerenes: a guest-induced enhancement of thixotropy.

Self-assembly behaviors of a series of systems (G1, G2, and G3) possessing same organic building blocks based on a substituted anthracene have been investigated in decalin. G2 and G3 are dominated by head-to-tail (ht) and head-to-head (hh) type dimers of G1, respectively. G1 gives a thermoresponsive gel that behaves ideally, showing frequency-independent elastic and viscous moduli. Interestingly, G2 produces a thixotropic gel that shows the signature of structural relaxation, signifying the dynamic nature of the system. In contrast, G3 remains fluidlike. As investigated by scanning electron microscopy (SEM), in the assembly process of G2, first disklike nanoaggregates are formed, and in the second step these aggregates interact to construct the densely packed secondary assembly. A transition from secondary assembly to primary assembly under shear initiates the mechanoresponsive destruction of the gel. In the self-assembly process, G1 propagates in a one-dimensional fashion, whereas G2 and G3 can propagate in a two-dimensionional fashion. The same side orientation of the substituents in G3 facilitates the formation of a compact closed-shell-type structure, which results in the generation of isolated nanocrystals. The long-range weak interaction together with the capability of propagating in two dimensions is found to be essential for the construction of such a mechanoresponsive assembly. C(60) and C(70) could be incorporated successfully in G2 assembly to develop mechanoresponsive fullerene assemblies. The presence of fullerenes not only enhances the elastic properties of G2 but also intensifies the thixotropy. C(70) appears to be a superior guest in terms of property enhancement due to its better size fitting with the concave-shaped host.

Weak gel of chitin with ionic liquid, 1-allyl-3-methylimidazolium bromide.

This paper reports the formation of weak gel of chitin with an ionic liquid, 1-allyl-3-methylimidazolium bromide (IL). When a mixture of 5% (w/w) chitin with IL was heated at 100 degrees C for 48h, the clear liquid was obtained. The experimental process was observed by the CCD camera view and the SEM analysis. From a mixture of chitin with IL in the higher concentration (7%, w/w), a more viscous material, i.e., a gel-like material was obtained. The rheological evaluations showed that both 5% (w/w) and 7% (w/w) chitins with IL behaved as weak gels.

Abnormal viscosity increment observed for an ionic liquid by dissolving lithium chloride.

The effect of adding an inorganic salt, lithium chloride, and water on the viscosity of an ionic liquid, 1-n-butyl-3-methylimidazolium chloride (BmimCl), was investigated by shear stress measurements with a rheometer. The shear rate dependence of the viscosity showed shear thinning behavior, which implies that some structure should exist in the liquid and the structure should change at high shear rates. Addition of LiCl enhances the viscosity of BmimCl. The logarithmic value of zero-shear viscosity, eta(0), of BmimCl increases linearly and largely with increasing added salt content. The increasing rate of the viscosity by addition of LiCl was about 10 times larger than that for an aqueous solution of LiCl. When water is added into BmimCl, viscosity decreased. The increasing rate of the viscosity by addition of LiCl for BmimCl with about 5 wt % of water was almost the same as that for BmimCl without addition of water.

Heat-set gel-like networks of lipophilic Co(II) triazole complexes in organic media and their thermochromic structural transitions.

A novel class of thermally responsive supramolecular assemblies is formed from the lipophilic cobalt(II) complexes of 4-alkylated 1,2,4-triazoles. When an ether linkage is introduced in the alkylchain moiety, a blue gel-like phase is formed in chloroform, even at very low concentration (ca. 0.01 wt %, at room temperature). The blue color is accompanied by a structured absorption around 580-730 nm, which is characteristic of cobalt (II) in the tetrahedral (T(d)) coordination. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) of the gel-like phase confirms the formation of networks of fibrous nanoassemblies with widths of 5-30 nm. The observed widths are larger than a molecular length of the triazole ligand (ca. 2.2 nm) and they are consisted of aggregates of T(d) coordination polymers. Very interestingly, the blue gel-like phase turned into a solution by cooling below 25 degrees C. A pale pink solution is obtained at 0 degrees C, indicating the formation of octahedral (O(h)) complexes. The observed thermochromic transition is totally reversible. The formation of gel-like networks by heating is contrary to the conventional organogels, which dissolve upon heating. Temperature dependence of the storage and loss moduli (G' and G") shows minima around at 27 degrees C, at which temperature they gave comparable values. On the other hand, G' exceeds G" both in the gel-like phase (temperature above 27 degrees C) and in the solution phase (temperature below 25 degrees C). These observations indicate that T(d) complexes are present as low-molecular weight species around at 25-27 degrees C. They are self-assembled to polymeric T(d) complexes by heating and form gel-like networks. Upon cooling the solution below 25 degrees C, T(d) complexes are converted to O(h) complexes and they also self-assemble into oligomeric or polymeric species at lower temperatures. The observed unique thermochromic transition (pink solution --> blue gel-like phase) is accompanied by an exothermic peak in differential scanning calorimetry (DSC), and is shown to be an enthalpy-driven process. The lipophilic modification of one-dimensional coordination systems provides unique solution properties and it would be widely applicable to the design of thermoresponsive, self-assembling molecular wires.