Syngas production by biomass gasification using Rh/CeO2/SiO2 catalysts and fluidized bed reactor

We have been developed novel catalysts for gasification of biomass with much higher energy efficiency than conventional methods (non-catalyst, dolomite, commercial steam reforming Ni catalyst). From the result of the gasification of cellulose over novel Rh/CeO₂/SiO₂ catalysts, it is found that the gasification process consists of the reforming of tar and the combustion of solid carbon. We also tested novel Rh/CeO₂/SiO₂ in the gasification with air, pyrogasification, and steam reforming of cedar wood. As a result, Rh/CeO₂/SiO₂ gave higher yield of syngas than the conventional steam reforming Ni catalyst. Furthermore, we compared the performance between single and dual bed reactors. Single bed reactor was effective in the gasification of cedar, however, it was not suitable for the gasification of rice straw since a rapid deactivation was observed. Gasification of rice straw, jute stick, baggase using the fluidized dual-bed reactor and Rh/CeO₂/SiO₂ was also investigated. Especially, the catalyst stability in the gasification of rice straw clearly was enhanced by using the fluidized dual bed reactor.     

High temperature catalytic combustion of methane and propane over hexaaluminate catalysts: NOx emission characteristics

Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH₄ and C₃H₈, in order to investigate the effect of the concentration of the fuels, O₂ and H₂O on NO_x emission and combustion characteristics. Among the hexaaluminate catalysts, Sr_0.8La_0.2MnAl₁₁O₁₉₋ prepared by the alkoxide method exhibited the highest activity for methane combustion and low NO_x emission capability. NO_x emission at 1500 °C was increased linearly with O₂ concentration, whereas water vapor addition decreased NO_x emission in CH₄ combustion over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst. In the catalytic combustion of C₃H₈ over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst, the amount of NO_x emitted was raised in the temperature range between 1000 and 1500 °C when the C₃H₈ concentration increased from 1 to 2 vol.%. It was found that NO_x emission in this temperature range was reduced effectively by adding water vapor.     

Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars

The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.     

Evaporation rate effect on starting point of shrinkage stress development during drying process in solvent cast polymer film

To reveal the effect of drying conditions on shrinkage stress existing between a film and a substrate, a polystyrene/toluene solution was coated on a glass substrate, and the volume fraction of toluene at the time when the stress starts to grow (?_S) was measured at various drying temperatures and evaporation rates. ?_S decreased with increase of drying temperature at a constant evaporation rate, while ?_S increased with increase of evaporation rate at a constant drying temperature. From these results, it was suggested that the dominant factors affecting the starting point of stress were both the chain mobility and the measurement time‐scale. Considering the two factors, the tendency of ?_S with the drying conditions is quite similar to that of the solvent content at glass transition point, and this fact indicates a strong correlation between the starting point of stress and the glass transition of coated solution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

An Additional Insight into the Correlation between the Distribution Ratios and the Aqueous Acidity of the TODGA System

Abstract

Extraction of Eu(III) and Am(III) from HNO₃ into the organic solvents using N,N,N′,N′‐tetraoctyl‐diglycolamide (TODGA) was investigated in order to study the detailed extraction reaction. The chemical species: 1:2 for metal:TODGA complex is present in polar diluents. On the other hand, the metal complexes need three or more TODGA molecules to remain stable in non‐polar diluents. The HNO₃ concentration dependence on the distribution ratio suggests that HNO₃ participates in the metal extraction. Infrared spectra indicate that the carbonyl oxygen coordinates with Eu(III), and luminescence lifetimes suggest that there are no water molecules in the inner coordination sphere of the extracted Eu‐complex.     

Fabrication of Functionally Graded SiO2‐Mo Material by Centrifugation and Floc‐Casting of Highly Concentrated Slurry

To fabricate functionally graded materials, a highly concentrated slurry of SiO₂‐Mo system was prepared and centrifugal force was applied in an attempt to achieve a graded composition. Subsequently, we formed a homogeneous green body with compositional gradation by floc‐casting at 80°C, which was then fired at 1750°C for 10 min in Ar. The sintered body had compositional ratios of SiO₂ and Mo as well as electrical conductivities that changed gradually along the direction of centrifugal force. The results demonstrate that centrifugation and control of slurry characteristics such as flocculation are effective in fabricating functionally graded SiO₂‐Mo materials.     

Structure of silane layer formed on silica particle surfaces by treatment with silane coupling agents having various functional groups

The surface treatment of spherical silica particles with silane coupling agents having various organic functional groups was conducted and the effect of the alkoxy group number on the molecular flexibility of the silane chain with multilayer coverage was investigated using ¹H-pulse nuclear magnetic resonance spectroscopy. The silica particles were treated with 2-propanol solution and heated at 120?°C for 24?h after solvent evaporation to accelerate the polycondensation reaction of silanol groups. For multilayer coverage, flexible linear chain and rigid network structures were expected to form on the surface from the di- and trialkoxy structures, respectively. However, the rigid network structure was formed from both the di- and trialkoxy structures with glycidoxy, amino, and methacryloxy functional silanes. Ring opening of the epoxy group occurred, followed by reaction to form the network structure, even with the dialkoxy structure of the glycidoxy functionality. Ring opening of the epoxy group could be reduced by pH adjustment of the treatment solution and the linear chain structure was formed from the dialkoxy structure. In the case of amino and methacryloxy functional groups, hydrogen bonds were formed between the amino or methacryloxy groups and the silanol groups on the silica surface or silane molecules.     

Neuroprotective Effects of Liraglutide for Stroke Model of Rats

The number of diabetes mellitus (DM) patients is increasing, and stroke is deeply associated with DM. Recently, neuroprotective effects of glucagon-like peptide-1 (GLP-1) are reported. In this study, we explored whether liraglutide, a GLP-1 analogue exerts therapeutic effects on a rat stroke model. Wistar rats received occlusion of the middle cerebral artery for 90 min. At one hour after reperfusion, liraglutide or saline was administered intraperitoneally. Modified Bederson’s test was performed at 1 and 24 h and, subsequently, rats were euthanized for histological investigation. Peripheral blood was obtained for measurement of blood glucose level and evaluation of oxidative stress. Brain tissues were collected to evaluate the level of vascular endothelial growth factor (VEGF). The behavioral scores of liraglutide-treated rats were significantly better than those of control rats. Infarct volumes of liraglutide-treated rats at were reduced, compared with those of control rats. The level of derivatives of reactive oxygen metabolite was lower in liraglutide-treated rats. VEGF level of liraglutide-treated rats in the cortex, but not in the striatum significantly increased, compared to that of control rats. In conclusion, this is the first study to demonstrate neuroprotective effects of liraglutide on cerebral ischemia through anti-oxidative effects and VEGF upregulation.     

High thermal stable thermoplastic-thermosetting polyimide film by use of asymmetric dianhydride (a-BPDA)

In order to obtain thermoplastic (before curing) and thermosetting (after curing) polyimides with high T_g for adhesive film, we prepared novel polyimides having phenylethynyl group in the side chain (44% of concentration of curing group) from asymmetric 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA), 3,4′-oxydianiline (3,4′-ODA) or 1,3-bis(4-aminophenoxy)benzene (1,3,4-APB) or 1,3-bis(3-aminophenoxy)benzene (1,3,3-APB), and 2,4-diamino-1-(4-phenylethynylphenoxy)benzene (mPDAp). Among three kinds of polymer, uncured polyimide of a-BPDA/1,3,4-APB; mPDAp had rather high T_g (265 °C, DMA) and thermoplasticity (E′ drop>10³ at T_g). After curing reaction of phenylethynyl group, the T_g of the polyimide was increased dramatically (364 °C, DMA). The polyimide derived from 1,3,4-APB having less concentration of curing group (20%) was also prepared to improve further film flexibility and toughness.     

Smart polyion complex micelles for targeted intracellular delivery of PEGylated antisense oligonucleotides containing acid-labile linkages

A novel pH-sensitive and targetable antisense ODN delivery system based on multimolecular assembly into polyion complex (PIC) micelles of poly(L-lysine) (PLL) and a lactosylated poly(ethylene glycol)-antisense ODN conjugate (Lac-PEG-ODN) containing an acid-labile linkage (beta-propionate) between the PEG and ODN segments has been developed. The PIC micelles thus prepared had clustered lactose moieties on their peripheries and achieved a significant antisense effect against luciferase gene expression in HuH-7 cells (hepatoma cells), far more efficiently than that produced by the nonmicelle systems (ODN and Lac-PEG-ODN) alone, as well as by the lactose-free PIC micelle. In line with this pronounced antisense effect, the lactosylated PIC micelles showed better uptake than the lactose-free PIC micelles into HuH-7 cells; this suggested the involvement of an asialoglycoprotein (ASGP) receptor-mediated endocytosis process. Furthermore, a significant decrease in the antisense effect (27 % inhibition) was observed for a lactosylated PIC micelle without an acid-labile linkage (thiomaleimide linkage); this suggested the release of the active (free) antisense ODN molecules into the cellular interior in response to the pH decrease in the endosomal compartment is a key process in the antisense effect. Use of branched poly(ethylenimine) (B-PEI) instead of the PLL for PIC micellization led to a substantial decrease in the antisense effect, probably due to the buffer effect of the B-PEI in the endosome compartment, preventing the cleavage of the acid-labile linkage in the conjugate. The approach reported here is expected to be useful for the construction of smart intracellular delivery systems for antisense ODNs with therapeutic value.