Preparation of Galactomannan-Based Materials Compatibilized with Ionic Liquids

This paper reports the preparation of galactomannan/ionic liquid composite materials from the corresponding ion gels. Three kinds of galactomannans, that is, fenugreek gum (FG), guar gum (GG), and locust bean gum (LBG) and an ionic liquid of 1-butyl-3-methylimidazolium chloride (BMIMCl) were used. When the galactomannan/BMIMCl gels were immersed in ethanol, followed by dryness under reduced pressure, the galactomannan/BMIMCl composite materials were obtained. The crystalline structures of galactomannans in the materials were evaluated by the powder X-ray diffraction measurement. The mechanical property of the FG/BMIMCl composite material under compressive mode was superior compared with the GG and LBG/BMIMCl composite materials. Then, FG films compatibilized with polymeric ionic liquids (PILs) were also prepared by in situ radical polymerization of polymerizable ionic liquids, 1-(3-acryloyloxypropyl)-3-vinylimidazolium bromide and 1-methyl-3-vinylbenzylimidazolium chloride by AIBN in mixtures of FG with BMIMCl. The mechanical properties of the resulting films were affected by the FG/PIL ratios as well as the unit ratios in PILs.     

Adjoint inverse modeling of NOx emissions over eastern China using satellite observations of NO2 vertical column densities

A four-dimensional variational data assimilation system for optimization of NO_x emissions (RC4-NO_x) was developed. A parameterized NO_x chemistry scheme was introduced into the RC4-NO_x system, and key parameters such as chemical production and loss terms of NO_x were calculated in advance using the Community Multiscale Air Quality (CMAQ) modeling system. RC4-NO_x was applied to optimize NO_x emissions over eastern China (EC) in July 1996, 1999, and 2002 using Global Ozone Monitoring Experiment (GOME) satellite observations of NO₂ vertical column densities (VCDs) and a priori emissions from the Regional Emission Inventory in Asia (REAS). After assimilation, RC4-NO_x generally reproduced the spatial distribution, regional averaged values, and time evolution of GOME NO₂ VCDs. Over EC, a priori emissions were reduced by 20% in 1996 and by 8% in 1999, whereas a posteriori emissions were almost the same as a priori emissions in 2002. A priori emissions in the Beijing region were reduced by optimization over the whole simulation period. A posteriori emissions over the Yangtze Delta were larger than a priori emissions in 2002, although they were smaller in both 1996 and 1999. As in other areas, a priori emissions over the North China Plain were reduced in 1996; but those over the eastern part of the plain were increased in 1999, and the area of increased emissions moved slightly westward in 2002. In each region, the growth rates of a posteriori emissions during both 1996–1999 and 1999–2002 became generally larger than those of a priori emissions, and the trends of a posteriori emissions became similar to those of GOME NO₂ VCDs. Our inverse modeling analysis indicates that the rate of increase of NO_x emissions over EC from 1996 to 2002 was much larger for a posteriori emissions (49%) than for a priori emissions (19%).     

Imposex in marine gastropods may be caused by binding of organotins to retinoid X receptor

Organotin compounds have been widely used as antifouling paints for ships and fishing nets since the 1960s and have thus been released into marine environments. Aquatic invertebrates, particularly marine gastropods, are extremely sensitive to organotin compounds such as tributyltin (TBT) and triphenyltin (TPT) and undergo changes in sexual identity in response to exposure. This worldwide phenomenon is one of the worst consequences of pollution by man-made chemicals and has led to the ban of such compounds in antifouling paints in a number of countries, although organotin compounds still exist in the environment. So far, very low-concentrations of TBT or TPT have been shown to induce imposex (superimposition of male genitalia on female) in marine gastropods. Although the imposex induction mechanism has been controversial for many years, it was recently reported that TBT and TPT are potent and efficacious activators of retinoid X receptor (RXR), a member of the nuclear receptor superfamily. In this review, I discuss the involvement of RXR in the development of gastropod imposex. Physical and Chemical Impacts on Marine Organisms, a Bilateral Seminar Italy–Japan held in November 2004     

Estimation of 1999-2004 dietary daily intake of PCDDs, PCDFs and dioxin-like PCBs by a total diet study in metropolitan Tokyo, Japan

A study of the dietary intake of dioxins, consisting of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) through foods retailed in the metropolitan Tokyo area from 1999 to 2004 was carried out by the total diet-market basket method on the basis of food classification (14 groups) and the data on food consumption in the Tokyo region obtained from the Japan Nutrition Survey. The daily intake of dioxins per kg of body weight for a 50 kg average adult body was 2.18 pg TEQ/kg/day in 1999, 1.87 pg TEQ/kg/day in 2000, 1.25 pg TEQ/kg/day in 2001, 1.60 pg TEQ/kg/day in 2002 and 2003 and 1.55 pg TEQ/kg/day in 2004, respectively. These amounts were less than the tolerable daily intake (TDI) of 4 pg TEQ/kg/day for dioxins established in Japan. The dioxins taken daily through fish and shellfish (group 10) accounted for more than 50% of sum WHO-TEQs. In addition, more than 90% of the daily intake of dioxins was taken through fish and shellfish (group 10), meat and eggs (group 11), milk and dairy products (group 12). Also, this study clearly showed that the ratio of dioxin-like PCBs in the daily intake of dioxins was increasing yearly because the reduction rate of dioxin-like PCBs was lower than that of PCDDs and PCDFs in foods.     

Preparation of Cellulose/Xanthan Gum Composite Films and Hydrogels Using Ionic Liquid

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.     

Preparation of Cationic/Anionic Chitin Nanofiber Composite Materials

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.     

Preparation of Natural Rubber/Condensed Tannin Semi-interpenetrating Polymer Network Composites by Hematin-Catalyzed Cross-Linking

In this study, the preparation of semi-interpenetrating polymer network (semi-IPN) composites composed of natural rubber and condensed tannin was performed by means of the enzyme-mimetic cross-linking of condensed tannin catalyzed by hematin. Prior to the preparation of the composites, the hematin-catalyzed cross-linking behavior of condensed tannin was evaluated by the TGA measurement. The TGA results indicated that condensed tannin was sufficiently cross-linked by the hematin-catalyzed reaction in the presence of appropriate amounts of 30% (w/v) H₂O₂ aq. to give the relatively thermostable materials. For the preparation of the composites, a solution of condensed tannin and hematin, and subsequently 30% (w/v) H₂O₂ aq. were added to natural rubber latex and the mixture was stirred at room temperature for 10 min to perform the cross-linking of condensed tannin, followed by drying of the reaction mixture at 50 °C for 5 h, which was subsequently put into a heat device and hot-pressed at 100 °C and 20 MPa for 20 min to give the semi-IPN composite. The tensile stress?Cstrain measurement of the composites was conducted to evaluate the mechanical properties, which were changeable depending on the weight ratios of natural rubber to condensed tannin and the amounts of 30% (w/v) H₂O₂ aq. Moreover, the miscibility of the cross-linked tannin with natural rubber in the composite was evaluated by the SEM measurement.     

Facile Preparation of Chitin/Cellulose Composite Films Using Ionic Liquids

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.     

Decomposition reactions of epoxy resin and polyetheretherketone resin in sub- and supercritical water

Epoxy resin and polyetheretherketone (PEEK) resin were decomposed into their monomers such as phenol, cresols, and their analogues by thermal treatment in sub- and supercritical water in a 10-ml tubing bomb reactor. The addition of basic compounds such as Na₂CO₃ was effective in promoting the decomposition reaction of the resins. In the reaction of epoxy resin, the yield of identified products reached 10% for the reaction at 703K over 1h. In the reaction of PEEK resin, the total yield of phenol and dibenzofuran reached 88% for the reaction at 703K over 3h. Chemical participation of water in the decomposition reaction was confirmed by the reaction of dinaphthylether.