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671.
GY Gor CJ Rasmussen AV Neimark 《Langmuir : the ACS journal of surfaces and colloids》2012,28(33):12100-12107
The mechanisms of hysteretic phase transformations in fluids confined to porous bodies depend on the size and shape of pores, as well as their connectivity. We present a Monte Carlo simulation study of capillary condensation and evaporation cycles in the course of Lennard-Jones fluid adsorption in the system of overlapping spherical pores. This model system mimics pore shape and connectivity in some mesoporous materials obtained by templating cubic surfactant mesophases or colloidal crystals. We show different mechanisms of capillary hysteresis depending on the size of the window between the pores. For the system with a small window, the hysteresis cycle is similar to that in a single spherical pore: capillary condensation takes place upon achieving the limit of stability of adsorption film and evaporation is triggered by cavitation. When the window is large enough, the capillary condensation shifts to a pressure higher than that of the isolated pore, and the possibility for the equilibrium mechanism of desorption is revealed. These finding may have important implications for practical problems of assessment of the pore size distributions in mesoporous materials with cagelike pore networks. 相似文献
672.
Gallyamov MO Mourran A Tartsch B Vinokur RA Nikitin LN Khokhlov AR Schaumburg K Möller M 《Physical chemistry chemical physics : PCCP》2006,8(22):2642-2649
Toroidal self-assembled structures of perfluorododecylnonadecane and perfluorotetradecyloctadecane have been deposited on mica and highly oriented pyrolytic graphite surfaces by exposure of the substrates to solutions of the (pefluoroalkyl)alkanes in supercritical carbon dioxide. Scanning force microscopy (SFM) images have displayed a high degree of regularity of these self-assembled nanoobjects regarding size, shape, and packing in a monolayer. Analysis of SFM images allowed us to estimate that each toroidal domain has an outer diameter of about 50 nm and consists of several thousands of molecules. We propose a simple model explaining the clustering of the molecules to objects with a finite size. The model based on the close-packing principles predicts formation of toroids, whose size is determined by the molecular geometry. Here, we consider the amphiphilic nature of the (perfluoroalkyl)alkane molecules in combination with incommensurable packing parameters of the alkyl- and the perfluoralkyl-segments to be a key factor for such a self-assembly. 相似文献
673.
Vanadium complex of 2-(2'-Pyridyl)-4,5-dicyanoimidazole showing spermicidal and cytotoxic properties
Less GB Ockwig NW Rasmussen PG Smith GD Keller LM Drach JC 《Inorganic chemistry》2006,45(18):7105-7110
Two complexes having the formulas VO(DCIPy)2(H2O).1.5H2O and VO(DCIPy)2(H2O).2MeOH have been synthesized and characterized (DCIPy = 2-(2'-pyridyl)-4,5-dicyanoimidazolato). The methanol solvated species has been studied by X-ray diffraction, and single crystals form in the space group P2(1)/n. The hydrated species was studied by electron paramagnetic resonance spectroscopy in both the solid state and in a frozen solution, and the values of A( parallel) examined using the additivity relationship. The hydrated species was shown to exhibit both spermicidal and cytoxic properties. 相似文献
674.
Ooi BL Søtofte I Sokolov MN Kozlova SG Rasmussen SB Nielsen LC Henriksen J 《Inorganic chemistry》2006,45(13):5008-5017
By treatment of Zn-reduced ethanolic solutions of NbCl5 with HCl in the presence of sulfide followed by cation-exchange chromatography, two oxo-sulfido niobium aqua ions, the red [Nb4(mu4-S)(mu2-O)5(H2O)10]4+ and the yellow-brown [Nb5(mu3-S)2(mu3-O)2(mu2-O)2(H2O)14]8+, were isolated. Both readily form their respective thiocyanate complexes, for which the structure for the former has been previously reported. Brown crystals of (Me2NH2)6[Nb5S2O4(NCS)14].3.5H2O (1) were isolated in the case of the latter, and the structure was determined by X-ray crystallography (space group: a = 15.4018(5) A, b = 21.1932(8) A, c = 22.0487(8) A, alpha=gamma = 90 degrees , beta = 103.4590(10) degrees , and R(1) = 0.0659). An unprecedented pentanuclear Nb5S2O48+ core is revealed in which short Nb-Nb distances (2.7995(8)-2.9111(8) A) are consistent with metal-metal bonding. A stopped-flow kinetic study of the 1:1 equilibration of NCS- with [Nb4(mu4-S)(mu2-O)5(H2O)10]4+ has been carried out. Equilibration rate constants are independent of [H(+)] in the range investigated (0.5-2.0 M) and at 25 degrees C; kf= 9.5 M(-1) s(-1), kaq = 2.6 x 10(-2) s(-1), and K = 365 M1). Conditions with first NCS- and then [Nb4(mu4-S)(mu2-O)5(H2O)10]4+ in excess revealed a statistical factor of 4, suggesting the presence of four kinetically equivalent Nb atoms. Attempts to study the 1:1 substitution of NCS- with [Nb5(mu3-S)2(mu3-O)2(mu2-O)2(H2O)14]8+ showed signs of saturation kinetics. Quantum chemical calculations using the density functional theory (DFT) approach were performed on both the Nb4O5S4+ and Nb5O4S28+ naked clusters. The highest occupied and lowest unoccupied molecular orbitals have dominant Nb(4d) character. The HOMO for Nb4O5S4+ is a nondegenerate fully filled MO, whereas for Nb5O4S28+, it is a nondegenerate partially filled MO with one unpaired electron. EPR spectroscopy on [Nb5(mu3-S)2(mu3-O)2(mu2-O)2(H2O)14]8+ shows that the molecule has total anisotropy (C2v), with all three tensors, gx= 2.399, gy= 1.975, and gz= 1.531, resolved. No hyperfine interaction expected from the nuclear moment of I = 9/2 for 93Nb was observed. 相似文献
675.
Martin Rasmussen 《Journal of Differential Equations》2009,246(6):2242-2263
Recently, the existence of Morse decompositions for nonautonomous dynamical systems was shown for three different time domains: the past, the future and—in the linear case—the entire time. In this article, notions of exponential dichotomy are discussed with respect to the three time domains. It is shown that an exponential dichotomy gives rise to an attractor-repeller pair in the projective space, which is a building block of a Morse decomposition. Moreover, based on the notions of exponential dichotomy, dichotomy spectra are introduced, and it is proved that the corresponding spectral manifolds lead to Morse decompositions in the projective space. 相似文献
676.
677.
N. C. R. Holme L. Nikolova T. B. Norris S. Hvilsted M. Pedersen R. H. Berg P. H. Rasmussen P. S. Ramanujam 《Macromolecular Symposia》1999,137(1):83-103
Azobenzenes can serve as model compounds for the study of transcis isomerization in more complex molecules. We have performed time-resolved spectroscopy in solutions containing free azobenzene chromophores and diols with a view to obtaining the energy levels and lifetimes of the excited states. A transition route based on experimental results for the theoretically calculated energy level scheme is proposed. Physical observations of surface relief in thin films of azobenzene polymers when irradiated with polarized light are reported. These include two beam polarization holographic observations and single beam transmission measurements through a mask, followed by atomic force microscope and profiler investigations. It is concluded that none of the prevalent theories can explain all the observed facts. 相似文献