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991.
992.
Influence of Solution Volume on the Dissolution Rate of Silicon Dioxide in Hydrofluoric Acid 下载免费PDF全文
Boris Shvartsev Danny Gelman Ilia Komissarov Alon Epshtein Dr. David Starosvetsky Prof. Yair Ein‐Eli 《Chemphyschem》2015,16(2):370-376
Experimental data and modeling of the dissolution of various Si/SiO2 thermal coatings in different volumes of hydrofluoric acid (HF) are reported. The rates of SiO2‐film dissolution, measured by means of various electrochemical techniques, and alteration in HF activity depend on the thickness of the film coating. Despite the small volumes (0.6–1.2 mL) of the HF solution, an effect of SiO2‐coating thickness on the dissolution rate was detected. To explain alterations detected in HF activity after SiO2 dissolution, spectroscopic analyses (NMR and FTIR) of the chemical composition of the solutions were conducted. This is associated with a modification in the chemical composition of the HF solution, which results in either the formation of an oxidized species in solution or the precipitation of dissolution products. HF2? accumulation in the HF solution, owing to SiO2 dissolution was identified as the source of the chemical alteration. 相似文献
993.
Computational Insights into the Charge Relaying Properties of β‐Turn Peptides in Protein Charge Transfers 下载免费PDF全文
Ru Zhang Dr. Jinxiang Liu Dr. Hongfang Yang Shoushan Wang Meng Zhang Prof. Dr. Yuxiang Bu 《Chemphyschem》2015,16(2):436-446
Density functional theory calculations suggest that β‐turn peptide segments can act as a novel dual‐relay elements to facilitate long‐range charge hopping transport in proteins, with the N terminus relaying electron hopping transfer and the C terminus relaying hole hopping migration. The electron‐ or hole‐binding ability of such a β‐turn is subject to the conformations of oligopeptides and lengths of its linking strands. On the one hand, strand extension at the C‐terminal end of a β‐turn considerably enhances the electron‐binding of the β‐turn N terminus, due to its unique electropositivity in the macro‐dipole, but does not enhance hole‐forming of the β‐turn C terminus because of competition from other sites within the β‐strand. On the other hand, strand extension at the N terminal end of the β‐turn greatly enhances hole‐binding of the β‐turn C terminus, due to its distinct electronegativity in the macro‐dipole, but does not considerably enhance electron‐binding ability of the N terminus because of the shared responsibility of other sites in the β‐strand. Thus, in the β‐hairpin structures, electron‐ or hole‐binding abilities of both termini of the β‐turn motif degenerate compared with those of the two hook structures, due to the decreased macro‐dipole polarity caused by the extending the two terminal strands. In general, the high polarity of a macro‐dipole always plays a principal role in determining charge‐relay properties through modifying the components and energies of the highest occupied and lowest unoccupied molecular orbitals of the β‐turn motif, whereas local dipoles with low polarity only play a cooperative assisting role. Further exploration is needed to identify other factors that influence relay properties in these protein motifs. 相似文献
994.
Silver‐Assisted Chemical Etching on Silicon with Polyvinylpyrrolidone‐Mediated Formation of Silver Dendrites 下载免费PDF全文
Metal‐assisted chemical etching (MaCE) on silicon (Si)—mediated by polyvinylpyrrolidone (PVP)—is systematically investigated herein. It is found that the morphologies and crystallographic natures of the grown silver (Ag) dendrites can be significantly modulated, with the presence of PVP in the MaCE process leading to the formation of faceted Ag dendrites preferentially along the (111) crystallographic phase, rather than along the (200) phase. Further explorations of the PVP‐mediated effect on Si etching are also revealed. In contrast to the aligned Si nanowires formed by MaCE without PVP addition, only distributed nanopores with sizes of 200 to 400 nm appear on the Si surfaces in the presence of PVP. The origin of surface polishing on Si in the PVP‐mediated MaCE process can be attributed to the distinct transport pathway of holes supplied by the Ag+ ions, where the holes are injected directly into the primary Ag seeds, rather than through Ag dendrites, thus leading to the isotropic etching of the Si surface. 相似文献
995.
A Molecular Platform for Multistate Near‐Infrared Electrochromism and Flip‐Flop,Flip‐Flap‐Flop,and Ternary Memory 下载免费PDF全文
Bin‐Bin Cui Jian‐Hong Tang Jiannian Yao Yu‐Wu Zhong 《Angewandte Chemie (International ed. in English)》2015,54(32):9192-9197
A diruthenium complex with a redox‐active amine bridge has been designed, synthesized, and studied by single‐crystal X‐ray analysis and DFT and TDDFT calculations. It shows three well‐separated redox processes with exclusive near‐infrared (NIR) absorbance at each redox state. The electropolymerized film of a related vinyl‐functionalized complex displays multistate NIR electrochromism with low operational potential, good contrast ratio, and long retention time. Flip‐flop, flip‐flap‐flop, and ternary memories have been realized by using the obtained film (ca. 15–20 nm thick) with three electrochemical inputs and three NIR optical outputs that each displays three levels of signal intensity. 相似文献
996.
Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides 下载免费PDF全文
Dr. Abdessamad Benidar Prof. Dr. Didier Bégué Dr. Falk Richter Prof. Dr. Claude Pouchan Prof. Dr. Mohammed Lahcini Dr. Jean‐Claude Guillemin 《Chemphyschem》2015,16(4):848-854
Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides. 相似文献
997.
Dr. Martin Schmidt Prof. Albert Masson Prof. Hai‐Ping Cheng Prof. Catherine Bréchignac 《Chemphyschem》2015,16(4):855-865
Adsorption and coadsorption studies on free silver clusters show that nitrogen physisorbs like rare gases, whereas oxygen chemisorbs with similarities and differences to bulk silver surfaces. Silver nanoparticles activate, or even dissociate adsorbed oxygen molecules. The global electron configurations of the adsorbent and adsorbate dominate the stability at small clusters. This is more important than geometry and site effects. Due to electronic shell effects and electron pairing, the activation of oxygen strongly varies with size. At more than 40 free electrons in the complex, such quantum effects start to blur. The size dependence becomes smoother and general trends govern the reactivity, which is driven by the interaction between the charge state of the nanoparticle and the charge transfer of the reaction. 相似文献
998.
Feng‐Yang Bai Xiao‐Le Zhu Zi‐Man Jia Xu Wang Yan‐Qiu Sun Prof. Rong‐Shun Wang Prof. Xiu‐Mei Pan 《Chemphyschem》2015,16(8):1768-1776
The mechanism and kinetics of the reactions of CF3COOCH2CH3, CF2HCOOCH3, and CF3COOCH3 with Cl and OH radicals are studied using the B3LYP, MP2, BHandHLYP, and M06‐2X methods with the 6‐311G(d,p) basis set. The study is further refined by using the CCSD(T) and QCISD(T)/6‐311++G(d,p) methods. Seven hydrogen‐abstraction channels are found. All the rate constants, computed by a dual‐level direct method with a small‐curvature tunneling correction, are in good agreement with the experimental data. The tunneling effect is found to be important for the calculated rate constants in the low‐temperature range. For the reaction of CF3COOCH2CH3+Cl, H‐abstraction from the CH2 group is found to be the dominant reaction channel. The standard enthalpies of formation for the species are also calculated. The Arrhenius expressions are fitted within 200–1000 K as kT(1)=8.4×10?20T 2.63exp(381.28/T), kT(2)=2.95×10?21T 3.13exp(?103.21/T), kT(3)=1.25×10?23T 3.37exp(791.98/T), and kT(4)=4.53×10?22T 3.07exp(465.00/T). 相似文献
999.
ZnO‐Coated Carbon Nanotubes: Inter‐Diffusion of Carboxyl Groups and Enhanced Photocurrent Generation 下载免费PDF全文
Chia‐I Hung Dr. Hua‐Chiang Wen Yao‐Cheng Lai Dr. Shih‐Hsin Chang Prof. Dr. Wu‐Ching Chou Prof. Dr. Wen‐Kuang Hsu 《Chemphyschem》2015,16(4):812-816
ZnO is a defect‐governed oxide and emits light at both visible and UV regimes. This work employs atomic layer deposition to produce oxide particles on oxygenated carbon nanotubes, and the composites only show emission profiles at short wavelengths. The quenching of defect‐related emissions at long wavelengths is verified, owing to carboxyl diffusion into oxygen vacancies, and doping is supported by ZnCO3 formation in oxide lattice. Fully coated tubes display an increased photocurrent and the quantum efficiency increases by 22 % relative to the bare nanotubes. 相似文献
1000.
We report a self‐propelled Janus silica micromotor as a motion‐based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self‐propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s?1. Biotin‐functionalized Janus micromotors can specifically capture and rapidly transport streptavidin‐modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self‐propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab‐on‐chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications. 相似文献