XAFS Analysis for Niobium Carbide Particle Growth on Silica Support During Preparation Process

SiO₂-supported NbC catalysts were prepared by using temperature-programmed reactions (TPR). XAFS analysis confirmed that Nb₂O₅ was reduced to NbO₂ in the first TPR stage and converted into NbC in the second TPR stage. Nb particles grew only in the second TPR stage. Formation of highly dispersed NbC particles on SiO₂ surfaces was achieved.     

Liposome‐Based in Vitro Evolution of Aminoacyl‐tRNA Synthetase for Enhanced Pyrrolysine Derivative Incorporation

Methanosarcina species pyrrolysyl‐tRNA synthetase (PylRS) attaches Pyl to its cognate amber suppressor tRNA. The introduction of two mutations (Y384F and Y306A) into PylRS was previously shown to generate a mutant, designated LysZ‐RS, that was able to attach N‐benzyloxycarbonyl‐L ‐lysine (LysZ) to its cognate tRNA. Despite the potential of LysZ derivatives, further LysZ‐RS engineering has not been performed; consequently, we aimed to generate LysZ‐RS mutants with improved LysZ incorporation activity through in vitro directed evolution. Using a liposome‐based in vitro compartmentalization (IVC) approach, we screened a randomly mutagenized gene library of LysZ‐RS and obtained a mutant that showed increased LysZ incorporation activity both in vitro and in vivo. The ease and high flexibility of liposome‐based IVC should enable the evolution of not only LysZ‐RS that can attach various LysZ derivatives but also of other enzymes involved in protein translation.     

ION-EXCHANGE PROPERTIES OF HYDROUS TITANIUM DIOXIDE WITH A FIBROUS FORM OBTAINED FROM POTASSIUM DITITANATE

ABSTRACT

Ion-exchange properties of a new type of hydrous titanium dioxide with a fibrous form, which was obtained from potassium dititanate (K₂O(TiO₂)2), have been studied. The pH titration curve snowed that this material behaved as a bifunctional ion-exchanger. Distribution coefficients of some divalent metal ions on this material were measured as a function of pH and the selectivity series were found to be Ba > Sr > Ca > Mg for alkaline earth metal ions and Cu > Zn > Mn > Co > Ni for divalent transition metal ions. Large separation factors were obtained between some metal ion pairs and the mutual separations such as Cu from Sr, Ca, Mg, Co and Ni, and Mg from Ba and Zn have been achieved on columns of this material.     

ADSORPTION BEHAVIOR OF COBALT( II) IONS ON LAYERED DIHYDROGEN TETRATITANATE HYDRATE FIBERS IN AQUEOUS SOLUTIONS IN THE RANGE FROM 298 to 523 K

The adsorption properties of cobalt(II) ions have been studied on layered dihydrogen tetratitanate hydrate fibers, H₂Ti₄O₉,?nH₂O, in the temperature range from 298 to 523?K. The distribution coefficients of the adsorption of cobalt (II) ions were increased with increasing temperatures up to 367?K, but were decreased in the temperature range between 367 and 523?K. The X-ray powder diffraction patterns of the fibers indicate that the fibers hold layer structure up to 367?K, but change to low crystalline anatase or its precursor above that temperature. It is notable that the material has the capability of cobalt (II) adsorption even at 523?K, although the maximum is present at 367?K.     

Investigation of the effect of surface phosphate ester dispersant on viscosity by coarse-grain modeling of BaTiO slurry

To understand the role of phosphate ester dispersant, we investigated the rheology of a BaTiO slurry. For the model case, a coarse-grain molecular dynamics (CGMD) simulation was performed with the butyral polymer didodecyl hydrogen phosphate (DHP) in the toluene/ethanol solvent. By systematically analyzing the effect of DHP from an atomic-scale first principle and from all-atom MD to microscale CGMD simulation, we investigated how the adsorption of a DHP dispersant on a BaTiO surface affects the microstructure rheology of a BaTiO slurry. The first-principle and all-atom MD simulation suggests that DHP molecules prefer to locate near the BaTiO surface. CGMD simulation shows a reduction in viscosity with an increase in dispersants, suggesting that the dispersant population near the BaTiO surface plays a key role in controlling the rheology of the BaTiO slurry. In this study, we propose an approach for understanding the BaTiO slurry with molecular-level simulations, which would be a useful tool for efficient optimization of slurry preparation.     

Preparation and photocatalytic activity of Keggin-ion tungstate and TiO2 hybrid layer-by-layer film composites

Keggin ions (PW₁₂O₄₀³⁻ (PW₁₂), SiW₁₂O₄₀⁴⁻ (SiW₁₂), H₂W₁₂O₄₀⁶⁻ (H₂W₁₂)) and TiO₂ hybrid thin films were prepared using the layer-by-layer method. Their photocatalytic activities were investigated using gaseous 2-propanol decomposition. All films were transparent in the visible wavelength range. For 2-propanol decomposition, H₂W₁₂ was the most effective for the combination with TiO₂ despite having the smallest TiO₂ deposition amount. The photocatalytic activity of the PW₁₂–TiO₂ hybrid film was increased 2.3 times by visible light with UV illumination. This increase was less remarkable for hybrid films of other Keggin ions, suggesting that the visible light excitation of reduced PW₁₂ plays an important role in the enhancement of 2-propanol decomposition.     

Water vapor barrier property of organic-silica nanocomposite derived from perhydropolysilazane on polyvinyl alcohol substrate

Poly(vinyl alcohol) membrane was coated with organic-silica nanocomposite derived from perhydropolysilazane. For organic composite part, polystyrene-block-poly(4-vinyl phenol) [SP], poly(tert-butyl acrylate-co-2-hydroxyethyl methacrylate) [BA] and poly(butyl methacrylate-co-2-hydroxyethyl methacrylate) [BMA] were used. Water vapor barrier property of coat membrane was measured at relative humidity = 96% by a cup method. The coat films of nanocomposites with SP-silica and BA-silica showed better water vapor barrier property than those of the silica coat film without organic polymer and BMA-silica composites. The surface morphologies of the coat films were investigated by scanning electron microscopy and atomic force microscopy. The addition of organic polymer to silica prevented the crack formation of coat layer on the substrate.     

Design,Synthesis, and Biological Evaluation of Lysine Demethylase 5 C Degraders

Lysine demethylase 5 C (KDM5C) controls epigenetic gene expression and is attracting great interest in the field of chemical epigenetics. KDM5C has emerged as a therapeutic target for anti-prostate cancer agents, and recently we identified triazole 1 as an inhibitor of KDM5C. Compound 1 exhibited highly potent KDM5C-inhibitory activity in in vitro enzyme assays, but did not show strong anticancer effects. Therefore, a different approach is needed for the development of anticancer agents targeting KDM5C. Here, we attempted to identify KDM5C degraders by focusing on a protein-knockdown strategy. Compound 3 b , which was designed based on compound 1 , degraded KDM5C and inhibited the growth of prostate cancer PC-3 cells more strongly than compound 1 . These findings suggest that KDM5C degraders are more effective as anticancer agents than compounds that only inhibit the catalytic activity of KDM5C.     

High‐Yield Preparation,Versatile Structural Modification,and Properties of Layered Cobalt Hydroxide Nanocones

A low‐cost oil bath synthetic route is presented to produce uniform and highly crystalline layered cobalt hydroxide nanocones (NCs) intercalated with dodecyl sulfate anions (C₁₂H₂₅OSO₃^?, DS^?). A new exfoliating procedure, by gradually unravelling/unzipping these NCs through heat treatment in formamide‐water binary solution, is developed to prepare unilamellar nanosheets. Moreover, the NCs can be readily modified with various inorganic or organic anions via a conventional anion‐exchange process at ambient temperature. The exchanged product, for example, NO₃^?–intercalated NCs, can be more easily and rapidly transformed into cobalt oxides (e.g., Co₃O₄ and CoO) than the original DS^?–intercalated form while retaining a conical feature. Both the cobalt hydroxide NCs and exfoliated nanosheets are electrochemically redoxable, exhibiting a Faradaic pseudocapacitive behavior. The magnetic measurements further reveal both antiferromagnetic behaviors for transformed Co₃O₄ and CoO NCs. Their Néel temperature values are lower than those of bulk oxides due to finite size and geometric confinement effect. The peculiar conical feature of NCs with a hollow interior and tunable layer spacing, as well as exfoliated unilamellar nanosheets with all surface area exposed, may show promise for potential applications in electrochemical energy storage and magnetic devices.     

Reactive extraction of diols with phenyl boronic acid and trioctylmethylammonium chloride as coextractants and quantitative structure–property relationship of their extraction behaviors

BACKGROUND: Diols that can be produced biologically have attracted much attention because of the increased cost of producing them chemically. The cost of separating the diols from the broth forms a major part of the total cost of microbial production. Reactive extraction using organoboronate is one promising method for recovering diols from the dilute aqueous solution. RESULTS: A basic investigation of solvent extraction of diols was conducted at 303 K employing phenylboronic acid and trioctylmethylammonium chloride as coextractants in the mixed solvent. Both the tetrahedral boronate anion complex and trigonal boronate neutral complex were extracted. 1,3‐diols and vicinal diols were extracted, but 1,4‐diol was not extracted. Extraction equilibrium constants were correlated with the enthalpies of formation of the complexes, which were calculated by molecular modeling with semi‐empirical molecular orbital calculations considering the solvent effect. CONCLUSION: The complex extraction behaviour of diols with phenylboronic acid and quaternary ammonium salt can be predicted by using the quantitative structure–property relationship (QSPR). Copyright © 2009 Society of Chemical Industry