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Noy A Zepeda S Orme CA Yeh Y De Yoreo JJ 《Journal of the American Chemical Society》2003,125(5):1356-1362
Intermolecular interactions drive the vast majority of condensed phase phenomena from molecular recognition to protein folding to particle adhesion. Complex energy barriers encountered in these interactions include contributions from van der Waals forces, hydrogen bonding, and solvent medium. With the spectacular exception of hydrophobic interactions, contributions from the medium are usually considered secondary. We report a variable temperature force microscopy study of the interactions between several hydrogen bonds in different solvents that challenges this point of view. Surprisingly, we observed an increase in the strength of the interaction between carboxylic acid groups in ethanol as the temperature increased. Moreover, when we switched to a nonpolar solvent we observed the opposite behavior: The binding force decreased as the temperature increased. Kinetic model of bond dissociation provided quantitative interpretation of our measurements. We attributed the observed phenomena to a large entropic contribution from the ordered solvent layers that are forming on the probe and sample surfaces upon detachment. The observed reversal in the force vs temperature trend is a manifestation of a transition between thermodynamic and kinetic regimes of unbinding predicted by the model. Our results indicate that entropic barriers dominated by the interactions of solvent molecules with the surface exist in a much wider variety of systems than previously thought. 相似文献
94.
We study the exact multiplicity and ordering properties of positive solutions of the p-Laplacian Dirichlet problem
95.
Yeh Lam 《应用数学学报(英文版)》2003,19(3):405-416
Geometric process (GP) was introduced by Lam[4,5], it is defined as a stochastic process {Xn, n = 1, 2,…} for which there exists a real number a > 0, such that {an-1 Xn, n = 1,2, …} forms a renewal process (RP). In this paper, we study some limit theorems in GP. We first derive the Wald equation for GP and then obtain the limit theorems of the age, residual life and the total life at t for a GP. A general limit theorem for Sn with a > 1 is also studied. Furthermore, we make a comparison between GP and RP, including the comparison of their limit distributions of the age, residual life and the total life at t. 相似文献
96.
This paper analyzes, and thus reveals the structure of the stable invariant subspace of the related Hamiltonian matrix arising from the measurement feedback H
-control problem. Using this, it presents another method for the verification of the admissibility of the controller derived by Doyle et al. in 1989. The method not only eliminates unnecessary assumptions on stabilizability and detectability, but also gives deeper insight into the relationship among the stable parts of the associated matrices. 相似文献
97.
Experimental observation of the slowdown of optical beams by a volume-index grating in a photorefractive LiNbO3 crystal 总被引:3,自引:0,他引:3
We investigate the group velocity of light in a one-dimensional volume-index grating inside a photorefractive LiNbO>(3) crystal. The slowdown of the group electromagnetic propagation is observed experimentally by tuning of the wave number of the optical beam close to the outside edge of the forbidden bandgap. We obtain a large group index of up to 7.5 in a 3.5-cm crystal sample. The group index is compared with the result of a theoretical derivation. The results are presented and discussed. 相似文献
98.
AbstractThe photochemical reactions of eight carbohydrate trifluoromethanesulfonates (triflates) have been investigated in methanol in the presence of potassium iodide. For those compounds which do not contain an aromatic chromophore, photolysis results in two types of reaction. One type produces deoxy sugars by replacement of the trifluoromethylsulfonyloxy (triflyloxy) group with a hydrogen atom. The second type of reaction generates partially protected sugars by replacement of the trifluoromethylsulfonyl (triflyl) group with a hydrogen atom. When the triflate being irradiated also has a protecting group containing an aromatic ring (i.e., benzyl, benzoyl, or p-tolylsulfonyl group), removal of the protecting group is the exclusive reaction pathway. 相似文献
99.
Extracting and concentrating mitochondrial protein complexes from gel strips after blue native PAGE (BN‐PAGE) can be daunting tasks using the traditional methods, such as electroelution, passive diffusion and centrifugal concentration. We present a simplified gel electrophoresis method to concentrate mitochondrial protein complexes with excellent recovery rate. Mitochondrial complex I present in a long gel strip from BN‐PAGE can be easily concentrated into a 0.8 cm gel strip when a second BN‐PAGE is performed with a Y‐shaped gel and the addition of 0.01% n‐dodecyl β‐D ‐maltoside and 0.001% SDS in the cathode buffer. Once completed, the concentrated protein complex in the gel strip is ready for SDS‐PAGE or proteomic studies. 相似文献
100.
The purpose of this paper is to apply a numerical technique in solving problems involving light beams in a random medium. The technique starts by generating numerically sample media with prescribed statistical properties. Rays are then traced in these sample media and the ray statistics are compiled. These statistics are utilized to find the mean square displacement and distribution of a beam. Problems on beam broadening and distortion of radiation patterns are considered. Fluctations in wave amplitude and phase are also investigated. When possible, the numerical results are compared with the analytical results and experimental results.It seems that the numerical technique has a potential to solve a great variety of problems. This is because it does not have severe restrictive conditions as those imposed on the analytic formulation. For example the technique is equally applicable when the irregularities are anisotropic, or when the background medium is inhomogeneous, or when the background is anistropic, or when there exist background wind. Some of these are discussed. 相似文献