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31.
Lau JK Wong CH Ng PS Siu FM Ma NL Tsang CW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3383-3396
The potassium cation affinities (PCAs) of 136 ligands (20 classes) in the gas phase were established by hybrid density functional theory calculations (B3-LYP with the 6-311+G(3df,2p) basis set). For these 136 ligands, 70 experimental values are available for comparison. Except for five specific PCA values-those of phenylalanine, cytosine, guanine, adenine (kinetic-method measurement), and Me(2)SO (by high-pressure mass spectrometric equilibrium measurement)-our theoretical estimates and the experimental affinities are in excellent agreement (mean absolute deviation (MAD) of 4.5 kJ mol(-1)). Comparisons with previously reported theoretical PCAs are also made. The effect of substituents on the modes of binding and the PCAs of unsubstituted parent ligands are discussed. Linear relations between Li+/Na+ and K+ affinities suggest that for the wide range of ligands studied here, the nature of binding between the cations and a given ligand is similar, and this allows the estimation of PCAs from known Li+ and/or Na+ affinities. Furthermore, empirical equations relating the PCAs of ligands with their dipole moments, polarizabilities (or molecular weights), and the number of binding sites were established. Such equations offer a simple method for estimating the PCAs of ligands not included in the present study. 相似文献
32.
To Fu Ma 《Mathematical Methods in the Applied Sciences》2001,24(8):583-594
In this paper, we study the equation under non‐linear boundary conditions which model the vibrations of a beam clamped at x=0 and supported by a non‐linear bearing at x=L. By adding only one damping mechanism at x=L, we prove the existence of a global solution and exponential decay of the energy. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
33.
We have analyzed the constant loss contribution to the ac conductivity in the frequency range 10 Hz-1 MHz and temperatures down to 8 K, for two Li ionic conductors, one crystalline (Li(0.18)La(0.61)TiO(3)) and the other glassy (61SiO(2);35Li(2)O.3Al(2)O3.P(2)O(5)). As temperature is increased a crossover is observed from a nearly constant loss to a fractional power law frequency dependence of the ac conductivity. At any fixed frequency omega, this crossover occurs at a temperature T such that omega approximately nu(0)exp(-E(m)/k(B)T), where nu(0) is the attempt frequency and E(m) is identified with the barrier for Li+ ions to leave their wells. 相似文献
34.
We study experimentally the jamming phenomenon of granular flow of monodisperse disks of D = 5 mm diameter in a two-dimensional hopper with opening R. The jamming probability J(d) is measured where d identical withR/D. We found that J(d) decreases from 1 to zero when d increases from 2 to 5. From observing the disk configurations of the arch in the jamming events, the jamming probability can be explained quantitatively by treating the arch as the trajectory of a restricted random walker. 相似文献
35.
36.
The fabrication of a novel sheathless interface for capillary electrophoresis–electrospray–mass spectrometry (CE–ESI–MS) is described. A programmable CO2 laser was used to ablate small channels in the walls of a polyimide capillary near the terminus. Subsequent exposure of the channel region to a cellulose acetate solution followed by drying resulted in the formation of an electrically conductive semi-permeable membrane. Application of an appropriate voltage to the reservoir resulted in the simultaneous establishment of an electrical connection for CE and ESI. Interface viability was demonstrated by conducting a CE separation of a peptide mixture, with detection accomplished via positive ion mode ESI–MS. For the peptide Val-Tyr-Val, a limit of detection of 0.1 femtomole (S/N 3) was achieved using single reaction monitoring. Attributes of the interface include structural robustness, ease of fabrication, minimal interface dead volume, and the ability to alter post-separation analyte ionization status by use of appropriate buffers in the interface reservoir. 相似文献
37.
Total internal reflection microscopy was used to directly measure the interaction potentials between a micron-sized silica sphere and a flat silica surface in the presence of a linear poly(N-isopropylacrylamide) (PNIPAM) aqueous solution. When the PNIPAM concentration was low, no discernible forces were detected. A further increase in PNIPAM concentration resulted in a long-range attraction which was likely due to a combined of the reduced electrostatic interaction between the silica particle and the flat surface after the polymer adsorption and polymer bridges formation. On the other hand, for a fixed PNIPAM concentration, the interaction potential profiles between the particle and flat surface were once again characterized by attraction as temperature was increased. This attractive force can be explained in terms of the conformational changes of PNIPAM chains at the surfaces, which subsequently affected the polymer adsorption and enhanced the segment–segment interaction among the adsorbed polymer chains. 相似文献
38.
Roland CM Fragiadakis D Coslovich D Capaccioli S Ngai KL 《The Journal of chemical physics》2010,133(12):124507
Various properties of vitrifying liquids are correlated with the dispersity of the dynamics, the latter reflected in the magnitude of the nonexponentiality parameter, β(K), describing the distribution of relaxation times. These properties include the mean relaxation time, τ(α), the fragility, and the dynamic crossover. The correlations with β(K) are observed in both experimental data and the results from molecular dynamics simulations on Lennard-Jones (LJ) type systems. Another, rather obvious property to correlate with β(K) is the dynamic heterogeneity, which can be quantified from the number of molecules, N(c), dynamically correlated over a time span τ(α). For a given LJ system, N(c) can be rigorously calculated and we find that it does indeed correlate with β(K) over a range of thermodynamic conditions. However, the analysis of experimental data for a broad range of real materials, wherein an approximation is required to obtain N(c), reveals the absence of any relationship between N(c) and β(K) among different materials. 相似文献
39.
D. D. Arslanov M. Spunei A. K. Y. Ngai S. M. Cristescu I. D. Lindsay S. T. Persijn K. J. Boller F. J. M. Harren 《Applied physics. B, Lasers and optics》2011,103(1):223-228
A fiber-amplified Distributed Bragg Reflector diode laser is used to pump a continuous wave, singly resonant Optical Parametric
Oscillator (OPO). The output radiation covers the 3–4 μm with ability of rapid (100 THz/s) and broad mode-hop-free tuning
(5 cm−1). Wavelength Modulation Spectroscopy is combined with the OPO to take optimal advantage of the spectral scan speed. The sensitivity
of the system was determined as 0.8 ppbv (parts-per-billion by volume) for ethane (C2H6) for the absorption peak at 2996.9 cm−1 recorded in 1.3 seconds, corresponding to a noise equivalent absorption sensitivity (NEAS) of 1.2×10−9 cm−1/Hz1/2. A comparison between results using the 1st, 2nd and 4th harmonic derivative signal from wavelength modulation was performed. The broad continuous tunability was demonstrated by
covering 35 cm−1 while recording absorption features of ethane, methane and water. 相似文献
40.