Thickening properties and emulsification mechanisms of new derivatives of polysaccharides in aqueous solution

The thickening properties of aqueous solutions of HHM-HEC (hydrophobically-hydrophilically modified hydroxyethylcellulose) and the emulsification mechanisms of HHM-HEC/water/oil systems were investigated. A dramatic increase in viscosity was observed with increased HHM-HEC concentration in water, caused by aggregation of hydrophobic alkyl chains. At higher concentrations of HHM-HEC (above 0.6 wt%) in water, it forms an elastic gel, which has good thixotropic properties and a high yield value. O/W (oil-in-water) type emulsions were obtained using HHM-HEC, which can emulsify various kinds of oil, including hydrocarbon, silicone, and perfluoropolymethylisopropyl ether. The viscosity of these emulsions depends only upon the oil volume fraction, not on the kind of oil. In addition, the oil particle size in the emulsions remained constant after a certain period because HHM-HEC formed a strong gel network structure and a protective layer, which prevented the emulsion from coalescing. Measurements of interfacial tension revealed that the alkyl chains in HHM-HEC did not significantly lower the interfacial tension at the water/oil interface when 0.5 wt% of HHM-HEC was added to water. Steady flow and oscillatory experimental results show that the rheological behavior of HHM-HEC/water/oil emulsions was similar to that of aqueous solutions of HHM-HEC. In the HHM-HEC/water/oil emulsion system, oil droplets were dispersed and kept stable in the strong gel structure of HHM-HEC. The aqueous solution of HHM-HEC showed salt resistance. It is thought to be due to sulfonic acid groups in HHM-HEC. The stability of the emulsion using HHM-HEC is based on both protective colloidal effects and associative thickening caused by alkyl chains in HHM-HEC.     

Reductive coupling of metal triangles in sandwich complexes

The one-electron reduction of [Pd3(C7H7)2(CH3CN)3][BF4]2 in acetonitrile resulted in the formation of the dimer dication [Pd6(C7H7)4(CH3CN)4][BF4]2, whose structure containing a novel bitriangle hexapalladium skeleton was determined by X-ray crystallographic analysis. The dimer is stable in CD3CN at ambient temperature for several days but is highly air-sensitive. Similarly, the cycloheptatriene tripalladium complex [Pd3(C7H7R)2(CH3CN)3][BF4]2 (R = H, t-Bu) dimerized upon one-electron reduction. Both monomer and dimer of cycloheptatriene complexes were structurally determined by X-ray crystallographic analyses.     

Microstructure evolution in Stöber-type silica nanoparticles and their in vitro apatite deposition

Prepared via Stöber-type sol–gel routes were three types of silica particles of <1 μm in size: pure silica, Ca-involving silica, and chitosan/alginate-coated silica with a polymershell-silica core structure. Calcium ions were impregnated in the organic layers of the polymer-coated silica particle. The sol–gel procedure was applied to tetraethoxysilane dissolved in an ethanol/water mixture, while Ca–silica was derived from CaCl₂-containing ethanol/water solutions. Scanning and transmission electron micrograph analyses indicated that those silica particles consisted of ~10 nm primary particles, the Ca–silica particles (~500 nm) were larger than the Ca-free ones (~200 nm) and that their size increased with the Ca concentration in the precursor solutions. From ¹H- and ²⁹Si- magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra and ²⁹Si cross-polarization NMR spectra, the mechanism of primary particle agglomeration and degradation of the secondary particles in saline were discussed in terms of the content of H₂O molecules and >Si–OH as well as hydrogen bonding interactions among them. In addition, the Ca–silica and core-shell silica deposited apatite in Kokubo’s simulated body fluid. Thus, the present Ca–silica and polymer-coated silica particles were suggested to be applicable to injectable bone fillers for bone generation.     

Synthesis and Characterization of Gelatin-Siloxane Hybrids Derived through Sol-Gel Procedure

A new type of inorganic-organic hybrid materials incorporating gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) was prepared through sol-gel processing. A solid-state ²⁹Si NMR analysis indicated that all the methoxy silane groups of GPSM were polymerized to yield —Si—O—Si— bridging bonds. An amino acid analysis confirmed grafting reactions of GPSM against gelatin chains. The increasing GPSM/gelatin ratio stimulated gel formation, phase separation, and the density of GPSM-crosslinking of the gelatin chains as well as it changed the micro- and macro- structures and the viscoelastic properties of the final products.     

Local Whittle likelihood estimators and tests for non-Gaussian stationary processes

In this paper, we propose a local Whittle likelihood estimator for spectral densities of non-Gaussian processes and a local Whittle likelihood ratio test statistic for the problem of testing whether the spectral density of a non-Gaussian stationary process belongs to a parametric family or not. Introducing a local Whittle likelihood of a spectral density f _θ (λ) around λ, we propose a local estimator [^(q)] = [^(q)] (l){\hat{\theta } = \hat{\theta } (\lambda ) } of θ which maximizes the local Whittle likelihood around λ, and use f_{[^(q)] (l)} (l){f_{\hat{\theta } (\lambda )} (\lambda )} as an estimator of the true spectral density. For the testing problem, we use a local Whittle likelihood ratio test statistic based on the local Whittle likelihood estimator. The asymptotics of these statistics are elucidated. It is shown that their asymptotic distributions do not depend on non-Gaussianity of the processes. Because our models include nonlinear stationary time series models, we can apply the results to stationary GARCH processes. Advantage of the proposed estimator is demonstrated by a few simulated numerical examples.     

Successful Application of Indirect Electrooxidation for the Transformation of Biaryl Methanols to the Corresponding Biaryl Ketones

Various biaryl methanols were electrooxidized into the corresponding biaryl ketones in good yields and under very mild reaction conditions. Because of the relatively high oxidation potential, bulky structure, and somewhat poor solubility, biaryl methanols do not readily undergo direct electrooxidative transformations as a synthetic step toward the corresponding biaryl ketones. Herein, we report the successful indirect electrooxidation of secondary biaryl methanols featuring the use of a slight excess amount of KI (1.2 equivalents, relative to the substrate) in MeOH.      

Photosensitive polybenzoxazole based on a poly(o‐hydroxy amide), a dissolution inhibitor,and a photoacid generator

A positive‐type photosensitive polybenzoxazole (PSPBO), based on a poly(o‐hydroxy amide) (PHA), the dissolution inhibitor (DI) 9,9‐bis(4‐tert‐butoxycarbonyloxyphenyl)fluorene (t‐Boc BHF), and the photoacid generator (5‐propylsulfonyloxyimino‐5H‐thiophene‐2‐ylidene)‐(2‐methylphenyl)acetonitrile (PTMA), was developed. Several new tert‐butoxycarbonylated compounds as DIs for PSPBOs were prepared from phenolic compounds having a cardolike structure with di‐tert‐butyl dicarbonate in the presence of 4‐dimethylaminopyridine. Among them, t‐Boc BHF and 5,5′,6,6′‐tetra(tert‐butoxycarbonyl)‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobiindane acted as excellent DIs, giving a large dissolution contrast between the exposed and unexposed areas in a 2.38 wt % tetramethylammonium hydroxide solution (TMAHaq)/5 wt % iso‐propanol (i‐PrOH). The dissolution behavior of this PSPBO system was studied in relation to the PTMA and t‐Boc BHF loadings and postexposure baking temperature. A PSPBO consisting of PHA (77 wt %), t‐Boc BHF (20 wt %), and PTMA (3 wt %) exhibited a sensitivity of 34 mJ/cm² and a contrast of 5.8 when exposed to 365‐nm light (i‐line) and developed with an aqueous alkaline developer, 2.38 wt % TMAHaq/5 wt % i‐PrOH. A clear, positive image with 6‐μm features and a 10‐μm‐thick pattern with high sensitivity and contrast was produced by contact printing and converted into polybenzoxazole patterns upon heating at 350 °C for 1 h. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 661–668, 2007     

Synthesis and In Vitro Behavior of Organically Modified Silicate Containing Ca Ions

Organically modified silicates containing calcium ion have a potential to bond to bone via an apatite layer deposited on their surfaces in the body environment. In this study, we examined the relationship between apatite deposition and the microstructure of the organically modified silicates synthesized from tetraethoxysilane (TEOS) and poly (dimethylsiloxane) (PDMS) with a different amount of calcium nitrate tetrahydrate (Ca(NO₃)₂·4H₂O) and hydrochloric acid (HCl). Apatite deposition was evaluated in vitro using a simulated body fluid (Kokubo solution). Copolymerization was confirmed between TEOS and PDMS even if PDMS free from —SiOH termination are used as one of the starting materials. The porosity and Ca content incorporated in the structure depended on the amount of HCl, whereas analysis of ²⁹Si MAS NMR spectra indicates that it caused few effects on the local structure around Si atoms. Apatite-forming ability is enhanced by optimal amounts of HCl and Ca (NO₃)₂·4H₂O. The difference in apatite-forming ability among the hybrid gels was attributed to both Ca(II) contents in the structure and aggregation states of the Si—OH groups. Better bioactivity of the hybrid gels is achieved by the release of Ca(II) ions trapped in structure at gelation and the formation of hydrated silica rich in Si—OH.     

Positive steady states for a prey-predator model with some nonlinear diffusion terms

This paper discusses a prey-predator system with strongly coupled nonlinear diffusion terms. We give a sufficient condition for the existence of positive steady state solutions. Our proof is based on the bifurcation theory. Some a priori estimates for steady state solutions will play an important role in the proof.