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11.
Several reports of experimentally derived proton affinity values and gas-phase basicity values for amino acids and peptides have recently appeared in the literature. Here, we show that the thermodynamic quantity that is measured by the Fourier transform mass spectrometry proton transfer bracketing of amino acids and peptides is gas-phase basicity and not proton affinity. Both experimental and theoretical evidence supports this conclusion. The difference between the values determined by proton transfer bracketing measurements for lysine versus leucine is consistent with a difference in gas-phase basicity rather than proton affinity. The rate of proton transfer from protonated lysine to a series of reference compounds have been measured. Entropy-driven, endothermic proton transfer is found to occur at the collision rate. Recent ab initio and semi-empirical calculations of the proton affinity of lysine are found to agree with the value that is derived from bracketing studies when one assumes that gas-phase basicity is measured. While entropy-driven reactions have been observed previously in high-pressure mass spectrometers, this is the first evidence for such reactions at low pressure in a Fourier transform mass spectrometer. 相似文献
12.
M. Gregory Oakes 《Metaphysica》2007,8(2):111-122
Causal realists maintain that the causal relation consists in “something more” than its relata. Specifying this relation in nonreductive terms is however notoriously difficult. Michael Tooley has advanced a plausible account avoiding some of the relation’s most obvious difficulties, particularly where these concern the notion of a cross-temporal “connection.” His account distinguishes discrete from nondiscrete causation, where the latter is suitable to the continuity of cross-temporal causation. I argue, however, that such accounts face conceptual difficulties dating from Zeno’s time. A Bergsonian resolution of these difficulties appears to entail that, for the causal realist, there can be no indirect causal relations of the sort envisioned by Tooley. A consequence of this discussion is that the causal realist must conceive all causal relations as ultimately direct. 相似文献
13.
A semiclassical reactive flux method for the calculation of condensed phase activated rate constants
A semi classical reactive flux algorithm for calculating thermally activated rate constants is presented which is based on a semi-classical transition state theory due to Chapman, Garrett and Miller [J. Chem. Phys. 63 (1975) 2710]. This reactive flux technique, when combined with the semiclassical TST, enables one to describe dynamical recrossings of the transition state on the same footing as tunneling effects. Most importantly, the method is readily applied to nonlinear multidimensional systems over a wide range of temperatures. It will be shown that the method works very well for a variety of existing models. 相似文献
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Real-time liquid crystal television-based technique for simulating optical wavefront distortion due to atmospheric turbulence is presented and demonstrated. A liquid crystal television (LCTV) operating in the “phase mostly” mode was used as an array of spatially correlated phase delays. A movie of the arrays in motion was then generated and displayed on the LCTV. The turbulence simulation system was verified by passing a collimated and doubled diode pumped Nd:YVO4 laser beam (532 nm) through the transparent LCTV screen. The beam was then passed through a lens and the power spectra of the turbulence information carrying beam was detected as a measure of the far-field distribution. The same collimated laser beam, without the LCTV, was also transmitted down an open-air range and the power spectra detected as a measure of a real far-field distribution. Accepted turbulence parameters were measured for both arrangements and then compared. 相似文献
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M. Carme Calderer M. Gregory Forest Qi Wang 《ournal of non Newtonian Fluid Mechanics》2004,120(1-3):69
We present a systematic derivation of hydrodynamic theories for nonhomogeneous nematic liquid crystal polymers (LCPs) by approximating the molecules as rigid ellipsoids, which can be either uniaxial molecules (spheroids) or biaxial ones. The short range interaction is assumed to be dominated by the excluded volume effect. Additional molecular properties with ellipsoidal molecules, e.g., a dipole–dipole interaction in extended nematics and chiral molecular structure in cholesterics, are accounted for through additional intermolecular potentials. Long-range molecular interaction is implemented through an averaged mean-field potential characterized by interaction functions. The extra elastic stress tensor is calculated using an extended virtual work principle consistent with conservation of angular momentum on the material volume, whereas the extra viscous stress is obtained by Batchelor’s volume averaging method. In the isothermal case, the theories are shown to satisfy the second law of thermodynamics, i.e., they admit positive production of entropy or energy dissipation. In the case of cholesterics, the kinetic theory reduces to the Leslie–Ericksen theory in the limit of weak translational diffusion, weak long range interaction, and weak flow. 相似文献
19.
Richard Arratia Bla Bollobs Gregory B. Sorkin 《Journal of Combinatorial Theory, Series B》2004,92(2):199-233
Motivated by circle graphs, and the enumeration of Euler circuits, we define a one-variable “interlace polynomial” for any graph. The polynomial satisfies a beautiful and unexpected reduction relation, quite different from the cut and fuse reduction characterizing the Tutte polynomial.It emerges that the interlace graph polynomial may be viewed as a special case of the Martin polynomial of an isotropic system, which underlies its connections with the circuit partition polynomial and the Kauffman brackets of a link diagram. The graph polynomial, in addition to being perhaps more broadly accessible than the Martin polynomial for isotropic systems, also has a two-variable generalization that is unknown for the Martin polynomial. We consider extremal properties of the interlace polynomial, its values for various special graphs, and evaluations which relate to basic graph properties such as the component and independence numbers. 相似文献
20.
The European Physical Journal C - We present the most recent high p T results from the CDF experiment using $p\overline{p}$ collisions at $\sqrt{s}=1.96~$ TeV produced at the Tevatron Collider at... 相似文献