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11.
Xin Wang Takashi Hisatomi Zheng Wang Jun Song Junle Qu Tsuyoshi Takata Kazunari Domen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10776-10780
LaTaON2 is a photocatalyst with intense visible light absorption up to 650 nm, but exhibits low H2 evolution activity owing to uncontrolled facets and high defect densities. In this work, core–shell‐structured plate‐like LaKNaTaO5/LaTaON2 was synthesized by nitriding a layered perovskite‐type LaKNaTaO5. The volatilization of K and Na species during the nitridation promoted the rapid transformation of LaKNaTaO5 into LaTaON2 along [010] direction with the plate‐like shape retained. This yielded high‐quality LaTaON2 shells exposing (010) facets on the lattice‐matched LaKNaTaO5 cores. After loading with a Rh co‐catalyst, LaKNaTaO5/LaTaON2 showed photocatalytic H2 evolution activity four times greater than that obtained from conventional irregular‐shaped LaTaON2 powders and utilized visible light up to 620 nm. This work provides a novel strategy yielding oxynitrides with well‐defined facets and low defect densities by selecting lattice‐matched oxide precursors containing volatile components. 相似文献
12.
Chisa Higuchi Hiromasa Tanaka Kazunari Yoshizawa 《Journal of computational chemistry》2019,40(1):164-171
The molecular mechanism of the adhesion between silica surface and epoxy resin under atmospheric conditions is investigated by periodic density-functional-theory (DFT) calculations. Slab models of the adhesion interface were built by integrating a fragment of epoxy resin and hydroxylated (0 0 1) surface of α-cristobalite in the presence of adsorbed water molecules. Effects of adsorbed water on the adhesion interaction are evaluated on the basis of geometry-optimized structures, adhesion energies, and forces. Calculated results demonstrate that adsorbed water molecules significantly reduce both the adhesion energies and forces of the silica surface–epoxy resin interface. The reduction of adhesion properties can be associated with structural deformation of water molecules confined in the tight space between the adhesive and adherend as well as structural flexibility of the hydrogen-bonding network in the interfacial region during detachment of the epoxy resin from the hydrophilic silica surface. © 2018 Wiley Periodicals, Inc. 相似文献
13.
Hydrogen bond complex stability between adenine (A) and hydrogen bond equivalents of uracil: 2-pyridone derivatives (UX
X2O) and 3-oxo-1,2,6-thiadiazine-1,1-dioxide derivatives (UX
SO2) was studied, and as the result, the hydrogen bond energy of UX
X2O-A and a complex of UXX
SO2-A, was about 1.5 kcal/mol more stable than that of the corresponding adenine-uracil derivatives complex, respectively. The energy difference between the imide tautomer and enol tautomer was smaller than those of uracil derivatives. UF
SO2 can form a stable complex with A, and its imide tautomer is stable. 相似文献
14.
Nakayama T Kamachi T Jitsumori K Omi R Hirotsu K Esaki N Kurihara T Yoshizawa K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8392-8402
The high substrate specificity of fluoroacetate dehalogenase was explored by using crystallographic analysis, fluorescence spectroscopy, and theoretical computations. A crystal structure for the Asp104Ala mutant of the enzyme from Burkholderia sp. FA1 complexed with fluoroacetate was determined at 1.2 ? resolution. The orientation and conformation of bound fluoroacetate is different from those in the crystal structure of the corresponding Asp110Asn mutant of the enzyme from Rhodopseudomonas palustris CGA009 reported recently (J. Am. Chem. Soc. 2011, 133, 7461). The fluorescence of the tryptophan residues of the wild-type and Trp150Phe mutant enzymes from Burkholderia sp. FA1 incubated with fluoroacetate and chloroacetate was measured to gain information on the environment of the tryptophan residues. The environments of the tryptophan residues were found to be different between the fluoroacetate- and chloroacetate-bound enzymes; this would come from different binding modes of these two substrates in the active site. Docking simulations and QM/MM optimizations were performed to predict favorable conformations and orientations of the substrates. The F atom of the substrate is oriented toward Arg108 in the most stable enzyme-fluoroacetate complex. This is a stable but unreactive conformation, in which the small O-C-F angle is not suitable for the S(N)2 displacement of the F(-) ion. The cleavage of the C-F bond is initiated by the conformational change of the substrate to a near attack conformation (NAC) in the active site. The second lowest energy conformation is appropriate for NAC; the C-O distance and the O-C-F angle are reasonable for the S(N) 2 reaction. The activation energy is greatly reduced in this conformation because of three hydrogen bonds between the leaving F atom and surrounding amino acid residues. Chloroacetate cannot reach the reactive conformation, due to the longer C-Cl bond; this results in an increase of the activation energy despite the weaker C-Cl bond. 相似文献
15.
16.
Kiyofumi Katagiri Keiko Ohta Kunihito Koumoto Kei Kurosu Yoshihiro Sasaki Kazunari Akiyoshi 《Colloid and polymer science》2013,291(6):1375-1380
Novel organic–inorganic hybrid nanoparticles consisting of polymer–hydrogel nanoparticles (nanogels) and iron oxide were developed for potential biomedical applications. Hybrid nanoparticles were prepared by a simple procedure using polysaccharide nanogels as a reactive site for iron oxide formation. The hybrid nanoparticles have a narrow size distribution with a diameter of approximately 30 nm and show high colloidal stability. These nanohybrid particles could be used as a contrast medium for magnetic resonance imaging or for magnetic hyperthermia therapy. 相似文献
17.
18.
The conductance through single 7,7,8,8‐tetracyanoquinodimethane (TCNQ) connected to gold electrodes is studied with the nonequilibrium Green’s function method combined with density functional theory. The aim of the study is to derive the effect of a dicyano anchor group, ?C(CN)2, on energy level alignment between the electrode Fermi level and a molecular energy level. The strong electron‐withdrawing nature of the dicyano anchor group lowers the LUMO level of TCNQ, resulting in an extremely small energy barrier for electron injection. At zero bias, electron transfer from electrodes easily occurs and, as a consequence, the anion radical state of TCNQ with a magnetic moment is formed. The unpaired electron in the TCNQ anion radical causes an exchange splitting between the spin‐α and spin‐β transmission spectra, allowing the single TCNQ junction to act as a spin‐filtering device. 相似文献
19.
γ-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride(MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride(SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. A novel ruthenium catalyst system consisting of Ru salts, trialkylphosphine and p-toluene sulfonic acid (p-TsOH) was found very effective for the hydrogenation of SAH affording GBL, which exhibited excellent catalyst performance, exceeding 97% selectivity for GBL and high activity. 相似文献
20.
Yasuhiko Iwasaki Shinpei Komatsu Tadashi Narita Kazunari Akiyoshi Kazuhiko Ishihara 《Macromolecular bioscience》2003,3(5):238-242
A vinyl‐functionalized polyphosphate (PIOP) was synthesized by ring‐opening polymerization of 2‐isopropyl‐2‐oxo‐1,3,2‐dioxaphospholane and 2‐(2‐oxo‐1,3,2‐dioxaphosphoroyloxyethyl methacrylate) with triisobutylaluminum as an initiator. The number‐averaged molecular weight of the PIOP was 1.2 × 104. The average number of vinyl groups in the PIOP is 2.20. Transparent hydrogels were prepared by the radical polymerization of 2‐methacryroyloxyethyl phosphorylcholine with PIOP as a cross‐linking reagent. These hydrogels may have many applications in the biomedical field because of their biodegradability and biocompatibility.