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961.
Brownson JR Tejedor-Tejedor MI Anderson MA 《The journal of physical chemistry. B》2006,110(25):12494-12499
The effects of pH and ultraviolet (UV) light with ligated formic acid on mesoporous TiO2 were characterized by transmission Fourier transform infrared (FTIR) spectroscopy and compared with adsorbed formate complexes. Surface-modified anatase thin films were prepared from acidic aqueous nanoparticulate anatase suspensions diluted with methanol and ethanol. Bands assigned to carboxylic acid groups displayed unique bonding character in the ligated formic acid on the anatase surface. For increased proton concentrations in the films, separation in -COO stretching bands (delta nu) for formic acid increased (increase in frequency for nuC=O and decrease in frequency for nuC-O). With UV exposure, surface-bound organics were rapidly removed by photocatalytic oxidation at 40 degrees C and 40% relative humidity (RH). In addition, the delta nu of the formic acid bands decreased as organics were mineralized to carbonates and CO2 with UV light. Aqueous formic acid adsorption experiments showed a distinctly different bonding environment lacking carbonate, and the delta nu for the carboxylic groups indicated a bridging bidentate coordination. The delta nu of the bands increased with increasing proton concentration, with both bands shifting to higher wavenumbers. The shifts may be ascribed to the influence of protonation on surface charge and the effect of that charge on the electronegativity of carboxylate groups bound to the surface. As alcohols are used in the mesoporous TiO2 solar cell preparation, implications of these surface modifications to dye-sensitized photovoltaics are discussed. 相似文献
962.
Grand-canonical transition-matrix Monte Carlo is combined with configurational-bias and expanded ensemble Monte Carlo techniques to obtain saturated densities and vapor pressures of select n-alkanes. Surface tension values for butane, hexane, and octane are also computed via the finite-size scaling method of Binder. The exponential-6 model of Errington and Panagiotopoulos is used to describe the molecular interactions. The effect of the number of configurational-bias trial conformations on the efficiency of phase equilibra calculations is studied. We find that a broad range of trial conformation numbers give reasonable performance, with the optimal value increasing with decreasing temperature for a fixed chain length. Phase coexistence properties are in good agreement with literature values and are obtained with very reasonable computing resources. Similar to other recently developed n-alkane force fields, the exponential-6 model overestimates the surface tension relative to experimental values. Statistical uncertainties for coexistence properties obtained with the current approach are relatively small compared to existing methods. 相似文献
963.
Joly AG Henyk M Beck KM Trevisanutto PE Sushko PV Hess WP Shluger AL 《The journal of physical chemistry. B》2006,110(37):18093-18096
Ultraviolet excitation of high surface area MgO films using 4.7 eV femtosecond pulses results in neutral Mg-atom desorption with hyperthermal kinetic energies in the range 0.1-0.4 eV. The Mg-atom hyperthermal energies and power dependences are similar to those previously observed using nanosecond pulsed excitation. Femtosecond two-pulse correlation measurements reveal the existence of different dynamical paths for Mg-atom desorption. One mechanism displays a sub-150 fs time scale and involves the simultaneous or near-simultaneous transition of two electrons to a 3-coordinated Mg(2+) site. Other paths display picosecond time scales that we associate with dynamics following electron trapping at 3-coordinated Mg(2+) surface sites. 相似文献
964.
Lewis acids control regioselectivity in the alkylation of epi-chlorohydrin and the stereochemistry of an alkyne addition to set the C24/C23 anti relationship. These advances facilitate an efficient total synthesis of bullatacin in 13.3% overall yield from commercial starting materials. 相似文献
965.
Manzamine A represents an important lead structure for the development of novel antimalarial chemotherapies. The synthesis and biological evaluation of a group of simplified analogues of manzamine A, which were designed to examine the roles of the A and D rings and of both the relative stereochemistry and the orientation of the beta-carboline heterocycle on the antimalarial activity of manzamine A, are described. [structure: see text] 相似文献
966.
[Structure: see text] An advanced intermediate in our planned synthesis of mitomycin C has been acquired in nine steps from tert-butyl glyoxylate. The aziridinyl pyrrolidine and quinone subunits are coupled regioselectively to arrive at an enamine that is prepared for C10 homologation. 相似文献
967.
In this Letter, we introduce a simple metal waveguide array for realizing all-angle wide frequency bandwidth negative refraction from the visible to infrared frequencies. Theoretical analysis from the rigorous coupled-wave theory reveals that the negative coupling constant resulting from the anomalous coupling of guided surface plasmon polariton modes contributes to the negative refraction. The analytical results are confirmed by finite-difference time-domain numerical simulations. Our result provides an alternative way to construct robust all-angle negative refractive materials operating in a wide range of frequency from the near-infrared to the visible range. 相似文献
968.
Let (G, K) be a Riemannian symmetric pair of maximal rank, where G is a compact simply connected Lie group and K is the fixed point set of an involutive automorphism σ. This induces an involutive automorphism τ of the based loop space Ω(G). There exists a maximal torus T ⊂ G such that the canonical action of T × S
1 on Ω(G) is compatible with τ (in the sense of Duistermaat). This allows us to formulate and prove a version of Duistermaat’s convexity theorem. Namely,
the images of Ω(G) and Ω(G)
τ
(fixed point set of τ) under the T × S
1 moment map on Ω(G) are equal. The space Ω(G)
τ
is homotopy equivalent to the loop space Ω(G/K) of the Riemannian symmetric space G/K. We prove a stronger form of a result of Bott and Samelson which relates the cohomology rings with coefficients in
\mathbbZ2 {\mathbb{Z}_2} of Ω(G) and Ω(G/K). Namely, the two cohomology rings are isomorphic, by a degree-halving isomorphism (Bott and Samelson [BS] had proved that the Betti numbers are equal). A version of this theorem involving equivariant cohomology is also proved.
The proof uses the notion of conjugation space in the sense of Hausmann, Holm, and Puppe [HHP]. 相似文献
969.
We consider the optimal replacement of a periodically inspected system under Markov deterioration that operates in a controlled environment. Provided are sufficient conditions that characterize an optimal control-limit replacement policy with respect to the system’s condition and its environment. The structure of the optimal policy is illustrated by a numerical example. 相似文献
970.
This paper proposes a Conditional Value-at-Risk Minimization (CVaRM) approach to optimize an insurer’s product mix. By incorporating the natural hedging strategy of Cox and Lin (2007) and the two-factor stochastic mortality model of Cairns et al. (2006b), we calculate an optimize product mix for insurance companies to hedge against the systematic mortality risk under parameter uncertainty. To reflect the importance of required profit, we further integrate the premium loading of systematic risk. We compare the hedging results to those using the duration match method of Wang et al. (forthcoming), and show that the proposed CVaRM approach has a narrower quantile of loss distribution after hedging—thereby effectively reducing systematic mortality risk for life insurance companies. 相似文献