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61.
H. Binder B. Kohlstrunk U. Brenn W. Schwieger G. Klose 《Colloid and polymer science》1998,276(12):1098-1109
Microcrystals of the metal silicate hydrate ilerite orient macroscopically on the surface of a ATR-crystals and thus, are
accessible for infrared linear dichroism measurements. We present first results which indicate that the alkyl chain packing
and the orientation of the polar group of dodecyltrimethylammoniumbromide (DTAB) intercalated between silicate layers can
be determined in terms of infrared order parameters. The properties of DTAB can be modulated by the relative humidity of the
surrounding atmosphere and by temperature. Upon heating DTAB undergoes a phase transition from a paraffin-like solid to a
fluid phase. The former is characterized by the orthorhombic perpendicular packing of the frozen alkyl chains with tilted
long axes. The interactions between the ionic groups of the surfactant and that of the host matrix stabilize the lamellar
arrangement of DTAB in the crystalline and in the fluid phases.
Received: 14 January 1998 Accepted: 27 July 1998 相似文献
62.
We present a unified approach for linear and nonlinear sensitivity analysis for models of reaction kinetics that are stated in terms of systems of ordinary differential equations (ODEs). The approach is based on the reformulation of the ODE problem as a density transport problem described by a Fokker-Planck equation. The resulting multidimensional partial differential equation is herein solved by extending the TRAIL algorithm originally introduced by Horenko and Weiser in the context of molecular dynamics (J. Comp. Chem. 2003, 24, 1921) and discussed it in comparison with Monte Carlo techniques. The extended TRAIL approach is fully adaptive and easily allows to study the influence of nonlinear dynamical effects. We illustrate the scheme in application to an enzyme-substrate model problem for sensitivity analysis w.r.t. to initial concentrations and parameter values. 相似文献
63.
《Surface and interface analysis : SIA》2003,35(12):991-997
In x‐ray photoelectron spectroscopy (XPS) the Auger parameter is often used to study the electronic properties of elements, particularly in insulator materials, because this parameter is assumed to be independent of charging effects. In this paper we report on subtle differences in sample structure and experimental conditions for which the sample potential may not remain constant during the measurements for some spectrometers or experimental arrangements; for such conditions the Auger parameter is not independent of charging. We compare a series of measurements with insulating plate substrates of Al2O3 on which different amounts of SnO2 and Au were deposited. X‐ray photoelectron spectra were collected for different conditions of the sample that was placed either grounded or left floating on a metallic sample holder during measurement. It is found that the Auger parameter is independent of the experimental conditions for Au but substantial differences were found for deposited SnO2. Surprisingly, measurement artifacts due to charging appeared in the Auger parameter for Sn when the sample holder was grounded but not when it was left floating. In the grounded samples differences up to 0.6 eV in the Auger parameter for Sn were found with respect to the actual value of this parameter measured with substrates where charging effects were not significant. Because no differences in peak broadening have been observed under different measurement conditions, it has been assumed that the shift was not caused by a conventional differential charging phenomenon. Considering the different response of the substrate and the deposited layer on stabilizing the charge when the sample is grounded, we have worked out a possible explanation to account for the observed artifacts. Instrumental specifications should be optimized very carefully, especially if (as here) relatively high charging shifts point to a non‐optimum self‐biasing of the surface potential at the insulating samples. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
64.
热重分析(TG)和微商热重法(DTG)广泛应用于各个研究领域,用非等温热重法测定固体化合物的热分解动力学参数已有报导.许多作者提出各种不同的数据处理方法.本文用的ρ-CH_3C_6H_4SR 型硫醚对钯的萃取具有选择性好、分配比高、气味较小、易溶于脂肪烃类溶剂、易于合成、是很有发展前途的一类萃取剂.我们合成五种ρ-CH_3C_6H_4SR(R:n-C_4H_9,n-C_6H_(13),n-C_8H_(17),n-C_(10)H_(21),n-C_(12)H_(25))型硫醚与钯(Ⅱ)的配合物,用TG-DTG 法研究它们的热分解过程,用微商法(Freeman-Carroll 方程)及积分法(Coats-Redfern 方程)获得了这些配合物的热分解动力学参数. 相似文献
65.
The surface behavior of solutions of the rhamnolipids, R1 and R2, were investigated in the absence and presence of an electrolyte (NaCl) through surface tension measurements and optical microscopy at pH 6.8. The NaCl concentrations studied are 0.05, 0.5 and 1 M. Electrolytes directly affect the carboxylate groups of the rhamnolipids. The solution/air interface has a net negative charge due to the dissociated carboxylate ions at pH 6.8 with strong repulsive electrostatic forces between the rhamnolipid molecules. This negative charge is shielded by the Na+ ions in the electrical double layer in the presence of NaCl, causing the formation of a close-packed monolayer, and a decrease in CMC, and surface tension values. The maximum compaction is observed at 0.5 M NaCl concentrations for R1 and R2 monolayers, with the R1 monolayer more compact than R2. The larger spaces left below the hydrophobic tails of R1 with respect to that of R2, due to the missing second rhamnosyl groups are thought to be responsible for the higher compaction. The rigidity of both R1 and R2 monolayers increases with the electrolyte concentration. The rigidity of the R1 monolayer is greater than that of R2 at all NaCl concentrations due to the lower hydrophilic character of R1. The variation of CMC values as a function of NaCl concentration obtained from the surface tension measurements and critical packing parameter (CPP) calculations show that spherical micelles, bilayer and rod like micelles are formed in the rhamnolipid solutions as a function of the NaCl concentration. The results of optical microscopy supported these aggregation states indicating lamellar nematic liquid crystal, cubic lamellar and hexagonal liquid crystal phases in R1 and R2 solutions depending on the NaCl concentration. 相似文献
66.
67.
Sonia E. Blanco 《Tetrahedron letters》2007,48(14):2577-2581
By applying the B3LYP/6-31G(d) method with the SCIPCM model on seven 4X substituted 2-hydroxybenzaldehydes, some structural characteristics related with their conformational equilibria and intramolecular hydrogen bonds have been clarified. The compounds are almost completely under the planar conformation characterized by a strong intramolecular hydrogen bond, which decreases in those solvents that possess a higher hydrogen bond donating capability and polarity. The substituents exert a marked influence on the conformational equilibrium constants and the strength of the IHB. Moreover, the excellent Hammett-type equations obtained support the proposed conformational reactions to quantify the IHB in the o-hydroxybenzaldehydes studied. 相似文献
68.
69.
Mu-Shih Lin Kuen-Tay Jeng Kun-Yui Huang Yen-Fong Shih 《Journal of polymer science. Part A, Polymer chemistry》1993,31(13):3317-3325
Simultaneous interpenetrating polymer networks (SINs) based on diglycidyl ether of bis-phenol A (DGEBA) and poly(ethylene glycol) diacrylate (PEGDA) in weight ratios of 100/0, 50/50, and 0/100 were blended and cured simultaneously by using benzoyl peroxide (BPO) and m-xylenediamine (MXDA) as curing agents. A kinetic study during SIN formation was carried out at 45, 55, 63, and 70°C. Concentration changes for both the epoxide and C?C bond were monitored with FTIR. A rate expression for DGEBA cure kinetics was established with a model reaction of phenyl glycidyl ether (PGE) and benzylamine. Experimental results revealed that lower rate constants and higher activation energy for the SIN were found, compared with those for the constituent DGEBA and PEGDA network formation. A model of network interlock was proposed to account for this phenomenon. During simultaneous cure of DGEBA and PEGDA, the interlock (mutual entanglement) between DGEBA and PEGDA networks provided a sterically hindered environment, which subsequently increased the activation energy and reduced cure rates for both DGEBA and PEGDA. © 1993 John Wiley & Sons, Inc. 相似文献
70.
The interlaboratory variability in the quantification of adsorbable organically bound halogens (AOX) in industrially contaminated
soil is presented. Three consecutive rounds of a proficiency testing scheme, in which between 88 and 119 routine laboratories
participated, yielded relative reproducibility standard deviations between 7 and 20% at AOX contents between 10.9 and 268 mg
kg−1. Nineteen laboratories with established proficiency were invited to participate in the certification of the AOX content in
three soil reference materials meant for the internal quality control in analytical laboratories. The certified values are
(1349 ± 59) mg kg−1, (80 ± 7) mg kg−1 and (102 ± 8) mg kg−1, respectively. 相似文献