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1.
ABSTRACT A new density functional for the study of associating inhomogeneous fluids based on Wertheim's first-order thermodynamic perturbation theory is presented and compared to the most currently used associating density functionals. This functional is developed using the weighted density approximation in the range of association of hard spheres. We implement this functional within the framework of classical density functional theory together with modified fundamental measure theory to account for volume exclusion of hard spheres. This approach is tested against molecular simulations from literature of pure associating hard spheres and mixtures of non-associationg and associating hard spheres with different number of bonding sites close to a hard uniform wall. Furthermore, we compare and review our results with the performance of associating functionals from literature, one based on fundamental measure theory and the inhomogeneous version of Wertheim's perturbation theory. Results obtained with classical DFT and the three functionals show excellent agreement with molecular simulations in systems with one hard wall. For the cases of small pores where only one or two layers of fluid are allowed discrepancies between results with classical DFT and molecular simulations were found. 相似文献
2.
We model the motion of a receptor on the membrane surface of a synapse as free Brownian motion in a planar domain with intermittent trappings in and escapes out of corrals with narrow openings. We compute the mean confinement time of the Brownian particle in the asymptotic limit of a narrow opening and calculate the probability to exit through a given small opening, when the boundary contains more than one. Using this approach, it is possible to describe the Brownian motion of a random particle in an environment containing domains with small openings by a coarse grained diffusion process. We use the results to estimate the confinement time as a function of the parameters and also the time it takes for a diffusing receptor to be anchored at its final destination on the postsynaptic membrane, after it is inserted in the membrane. This approach provides a framework for the theoretical study of receptor trafficking on membranes. This process underlies synaptic plasticity, which relates to learning and memory. In particular, it is believed that the memory state in the brain is stored primarily in the pattern of synaptic weight values, which are controlled by neuronal activity. At a molecular level, the synaptic weight is determined by the number and properties of protein channels (receptors) on the synapse. The synaptic receptors are trafficked in and out of synapses by a diffusion process. Following their synthesis in the endoplasmic reticulum, receptors are trafficked to their postsynaptic sites on dendrites and axons. In this model the receptors are first inserted into the extrasynaptic plasma membrane and then random walk in and out of corrals through narrow openings on their way to their final destination. 相似文献
3.
Nicholas W. DeLuca Yossef A. Elabd 《Journal of Polymer Science.Polymer Physics》2006,44(16):2201-2225
The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006 相似文献
4.
水溶性聚酯的结构和性能 总被引:2,自引:0,他引:2
由对苯二甲酸二甲酯、间苯二甲酸、间苯二甲酸二甲酯5-磺酸钠与乙二醇等共缩聚合成的PET型水溶性聚酯(WSP)是一种新型的水溶性聚合物,在化纤、纺织、涂料、粘合剂、电子、油墨等领域有着广泛的应用前景.化纤领域超细纤维新材料的研究、开发和生产,迫切需要一... 相似文献
5.
6.
聚电解质溶液中2.6-ANS探针的荧光谱研究 总被引:1,自引:0,他引:1
本文合成了2.6—ANS荧光探针分子,并在含有不同外加盐的NaPSS溶液中测定了探针的荧光发射光谱。结果表明:探针的荧光强度随Cs增大而增大,而探针光谱的最大发射波长和半波宽度随Cs增大而减小。当Cs达到一定值时,荧光谱参数与Cs关系曲线出现转折点,此时聚离了链以“类胶束”状态存在。 相似文献
7.
We investigate the construction of long, stable hybrid threadlike micelles consisting of polyelectrolytes and oppositely charged surfactants in aqueous solution and examine the physicochemical features such as their structure and viscoelastic behavior in aqueous solution. The most important point for their construction is the careful control of interactions, especially electrostatic interactions, caused between the surfactants and polyelectrolytes. Incorporated polyelectrolytes are fully extended in these hybrid threadlike micelles irrespective of the molecular weight of the polymer. The viscoelastic behavior of the hybrid threadlike micellar solution is similar to that of ordinary threadlike micellar systems consisting of low‐molecular‐weight substances. However, the inclusion of polymers in the micelles causes differences in their mechanical properties. 相似文献
8.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献
9.
N. SanzJ. Zaccaro L. DelmotteC. Le Luyer A. Ibanez 《Journal of solid state chemistry》2002,165(1):25-34
Organic nanocrystals of N-4-nitrophenyl-l-prolinol (NPP) have been grown in sol-gel matrices prepared from silicon alkoxide precursors. Our process is based on the control of the nucleation and growth kinetics of the dye in the pores of dense gels. Nanocomposites gel-glasses are obtained with a high optical quality due to the small size of the nanocrystals (10-20 nm). Differential scanning calorimetry experiments evidenced clearly the melting point of NPP nanocrystals, which is registered 51°C above that of NPP powder. Micro-Raman and solid state NMR spectroscopies allowed us to demonstrate that our nanocrystallization process does not chemically modify NPP molecules. We specified also the nature of interactions existing between the NPP nanocrystals and the xerogels. These strong interactions, which explain the important increase of the melting point of the nanocrystals in comparison to the NPP powder, are hydrogen bonds between nitro groups of NPP and uncondensed silanol functions of the silicate network. 相似文献
10.
Highly hydrophobically modified (with n-dodecylamide chain) linear poly(acrylic acid)s (HHMPAAH) and poly(sodium acrylate)s (HHMPAANa) with various degrees of grafting
(τ) were synthesized and used as emulsifiers of the n-dodecane/water system. The type of emulsion, oil in water (O/W) or water in oil (W/O), was investigated as a function of
the polymer chemical structure (τ, salt or acid form of the copolymer) and aqueous phase electrolyte concentration (NaNO3). Increasing τ and/or salt concentration was found to favor the formation of inverse emulsions. Direct liquid–liquid dispersions
are more likely to form with poly(sodium acrylate)s than with poly(acrylic acid)s. Hence, field variables such as τ, pH and
ionic strength are relevant parameters to control emulsion type. Moreover, a balanced polyelectrolyte neither soluble in oil
nor in water was synthesized for the first time. With this original emulsifier, the dispersion type was found to change from
O/W to W/O with polymer salting out. The work provides convenient model system for fundamental studies of polymer conformation
at liquid–liquid interfaces.
Received: 31 March 1998 Accepted: 30 April 1998 相似文献