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961.
Hessel L. Castricum Ashima Sah Jan A. J. Geenevasen Robert Kreiter Dave H. A. Blank Jaap F. Vente Johan E. ten Elshof 《Journal of Sol-Gel Science and Technology》2008,48(1-2):11-17
A procedure for the preparation of hybrid sols for the synthesis of organic–inorganic microporous materials and thin film membranes is reported. We describe silane reactivity and sol structure for acid-catalysed colloidal sols from mixtures of either tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES), or bis(triethoxysilyl)ethane (BTESE) and MTES. Early-stage hydrolysis and condensation rates of the individual silane precursors were followed with 29Si liquid NMR and structural characteristics of more developed sols were studied with Dynamic Light Scattering. Condensation was found to proceed at more or less similar rates for the different precursors. Homogeneously mixed hybrid colloids can therefore be formed from precursor mixtures. The conditions of preparation under which clear sols with low viscosity could be formed from BTESE/MTES were determined. These sols were synthesised at moderate water/silane and acid/silane ratios and could be applied for the coating of defect-free microporous membranes for molecular separations under hydrothermal conditions. 相似文献
962.
Conditions are given under which the empirical copula process associated with a random sample from a bivariate continuous distribution has a smaller asymptotic covariance function than the standard empirical process based on observations from the copula. Illustrations are provided and consequences for inference are outlined. 相似文献
963.
964.
965.
Ali Amran Stig E. Friberg Johan Sjöblom 《Journal of Dispersion Science and Technology》2013,34(5):621-632
NMR spectra were recorded of the silicon species obtained in the reaction between tetraethoxysilane and calcium nitrate hydrate in ethanol. The tetraethoxysilane reacted with a maximum of three of the four waters of hydration of the calcium nitrate at room temperature within a few days. The fourth water reacted after extended times (33 days) at room temperature or at enhanced temperature (60°C) within 24 hours. Samples with less than sufficient water for a complete reaction showed the corresponding amount of unreacted tetraethoxysilane. The calcium nitrate stayed colloidally dispersed within the ethanol silica gel and remained so even after the ethanol was removed. 相似文献
967.
968.
Application of 204mPb perturbed angular correlation of γ-rays spectroscopy in coordination chemistry
Vibenholt J Schau-Magnussen M Stachura M Bjerrum MJ Thulstrup PW Arcisauskaite V Hemmingsen L 《Inorganic chemistry》2012,51(4):1992-1994
(204m)Pb perturbed angular correlation of γ-rays (PAC) spectroscopy has been applied successfully for the first time to detect the nuclear quadrupole interaction in a lead(II) coordination compound in a molecular crystal [tetraphenylarsonium lead(II) isomaleonitriledithiolate ([AsPh(4)](4)[Pb(2)(i-mnt)(4)])]. The recorded parameters from a powder crystalline sample are ν(Q) = 0.178(1) GHz and η = 0.970(7). The electric field gradient (EFG) was determined at the PW91/QZ4P level including relativistic effects using the two-component zeroth-order regular approximation method for both the [Pb(i-mnt)(2)](2-) monomer and the [Pb(2)(i-mnt)(4)](4-) dimer. Only the EFG for the latter compares favorably with the experimental data, indicating that the picture of this complex as a prototypical hemidirected coordination geometry with a stereochemically active lone pair on lead(II) is inadequate. Advantages and limitations of (204m)Pb PAC spectroscopy as a novel technique to elucidate the electronic and molecular structures of lead-containing complexes and biomolecules are presented. 相似文献
969.
Sillrén P Bielecki J Mattsson J Börjesson L Matic A 《The Journal of chemical physics》2012,136(9):094514
We here present a statistical model of hydrogen bond induced network structures in liquid alcohols. The model generalises the Andersson-Schulz-Flory chain model to allow also for branched structures. Two bonding probabilities are assigned to each hydroxyl group oxygen, where the first is the probability of a lone pair accepting an H-bond and the second is the probability that given this bond also the second lone pair is bonded. The average hydroxyl group cluster size, cluster size distribution, and the number of branches and leaves in the tree-like network clusters are directly determined from these probabilities. The applicability of the model is tested by comparison to cluster size distributions and bonding probabilities obtained from Monte Carlo simulations of the monoalcohols methanol, propanol, butanol, and propylene glycol monomethyl ether, the di-alcohol propylene glycol, and the tri-alcohol glycerol. We find that the tree model can reproduce the cluster size distributions and the bonding probabilities for both mono- and poly-alcohols, showing the branched nature of the OH-clusters in these liquids. Thus, this statistical model is a useful tool to better understand the structure of network forming hydrogen bonded liquids. The model can be applied to experimental data, allowing the topology of the clusters to be determined from such studies. 相似文献
970.
Structural dynamics in liquid water slow down dramatically in the supercooled regime. To shed further light on the origin of this super-Arrhenius temperature dependence, we report high-precision (17)O and (2)H NMR relaxation data for H(2)O and D(2)O, respectively, down to 37 K below the equilibrium freezing point. With the aid of molecular dynamics (MD) simulations, we provide a detailed analysis of the rotational motions probed by the NMR experiments. The NMR-derived rotational correlation time τ(R) is the integral of a time correlation function (TCF) that, after a subpicosecond librational decay, can be described as a sum of two exponentials. Using a coarse-graining algorithm to map the MD trajectory on a continuous-time random walk (CTRW) in angular space, we show that the slowest TCF component can be attributed to large-angle molecular jumps. The mean jump angle is ~48° at all temperatures and the waiting time distribution is non-exponential, implying dynamical heterogeneity. We have previously used an analogous CTRW model to analyze quasielastic neutron scattering data from supercooled water. Although the translational and rotational waiting times are of similar magnitude, most translational jumps are not synchronized with a rotational jump of the same molecule. The rotational waiting time has a stronger temperature dependence than the translation one, consistent with the strong increase of the experimentally derived product τ(R)?D(T) at low temperatures. The present CTRW jump model is related to, but differs in essential ways from the extended jump model proposed by Laage and co-workers. Our analysis traces the super-Arrhenius temperature dependence of τ(R) to the rotational waiting time. We present arguments against interpreting this temperature dependence in terms of mode-coupling theory or in terms of mixture models of water structure. 相似文献