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951.
Ohsuna T Slater B Gao F Yu J Sakamoto Y Zhu G Terasaki O Vaughan DE Qiu S Catlow CR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5031-5040
High-resolution electron microscopy (HREM) has been used to image the surface structure of nano- and micrometer-sized synthetic crystals of zeolite-Linde-L (LTL). Columnar holes and rotational, nano-sized, wheel-like defects were observed within the crystals, where the hole has a minimum size equal to that of the rotational defect. Predictions of surface structure from atomistic computer simulation concur with the observations from HREM and provide insight into the crystal growth mechanism of perfect and defective LTL. Analysis of the energetics of the formation of rotational defect structures reveals that the driving force for defect creation is thermodynamic and furthermore, the rotational defects could be created in high concentrations. Formation of a columnar hole is found to be slightly energetically unfavourable and therefore we speculate that the incidence of both rotational and nano-sized vacancy defects is strongly dependent on kinetic factors and reaction conditions. The morphology of nano- and microcrystalline LTL is contradistinct and we use insights from simulation to propose an explanation of the disparity in crystal shape. 相似文献
952.
Xiang‐Gao Meng Chun‐Shan Zhou Li Wang Chang‐Lin Liu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o667-o670
5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C5H7N2+·C7H5O6S−·H2O or 3‐APy·5‐SSA·H2O, (I), and the anhydrous adduct, C5H7N2+·C7H5O6S− or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively. 相似文献
953.
Chang–Guo Zhan 《International journal of quantum chemistry》1992,44(2):123-140
This paper provides a brief and systematic presentation of the basic principle and method of the maximum overlap symmetry molecular orbital (MOSMO ) model and its application to simplification of molecular orbital calculation and to calculation of molecular structures and properties, together with some new results about the MOSMO calculation and new insights concerning the further extension of the principle and method. It has been shown that the theoretical method of the MOSMO model is very simple, reliable, and useful and can be employed to study the structure–property relation in even very large molecular systems. The numerical results obtained from the MOSMO calculation on various semiempirical molecular orbital approximation levels show that when the same parametrization, such as one of those employed in EHMO , CNDO /2, and HMO methods, is adopted, the MOSMOS are very close to the canonical molecular orbitals obtained from the customary LCAO method and the MOSMO calculation requires less computing time than does the LCAO method. The MOSMO calculation can be used for rapidly obtaining reasonably good molecular geometries, vibrational frequencies, and other properties of molecules by employing a simple improved semiempirical parametrization. Equilibrium geometries, vibrational frequencies, and other results are in good agreement with the experimental data and the results obtained from ab initio molecular orbital calculation. The basic calculational procedure of the MOSMO model can be extended further and has been employed to give some new results, to propose some new theoretical schemes and principles, and to introduce some new interesting theoretical problems that deserve to be studied further. 相似文献
954.
A simple and sensitive HPLC method for quantitative determination of guanidine in high salt and protein matrices was developed. The HPLC system consisted of an Agilent 1100 pump with an online degasser, a UV detector, an autosampler, and Dionex CS 14 cation-exchange guard (4 mm x 50 mm) and analytical (4 mm x 250 mm) columns. The mobile phase was 3.75 mM methanesulfonic acid (MSA) with a flow rate of 1 mL/min. The other analysis parameters were: 50 microL injection volume, 195 nm UV detection, and 21 min runtime. The limit of quantitation (LOQ) for guanidine HCl was determined to be 0.25 mg/L and the standard curve ranged from 0.25 mg/L to 10 mg/L. Sample preparation was required for the samples containing high protein concentrations. Proteins were removed by centrifuging a sample in a 30 K NanoSep centrifugal filter at 15,300 x g for 20 min. The method could determine guanidine accurately in sample matrices containing up to 200 mM sodium ion or up to 50 mM potassium ion. The method can be used for clearance testing of guanidine in biopharmaceutical products. 相似文献
955.
Ramiro Pino Olivier Bokanowski Eduardo V. Ludeña Roberto López Boada 《Theoretical chemistry accounts》2007,118(3):557-561
Bearing in mind the insight into the Hohenberg–Kohn theorem for Coulomb systems provided recently by Kryachko (Int J Quantum
Chem 103:818, 2005), we present a re-statement of this theorem through an elaboration on Lieb’s proof as well as an extension
of this theorem to finite subspaces.
Contribution to the Serafin Fraga Memorial Issue. 相似文献
956.
CaF_2在熔化以前为超离子导体相。一些实验和理论的研究表明,在超离子导体相中,Ca~(2+)仍维持原有的面心立方骨架,而F~-则在Ca~(2+)骨架中运动。早期的分子动力学模拟结果表明Ca~(2+)的均方根位移仅约0.3A,而F~-的扩散系数可达2.6×10~(-5)cm·s~(-1),已是熔盐扩散系数量级。近年来的中子散射实验表明在扩散离子和近邻离子间存在着某种动力学相关。为解释这些事实,新近Gillan的分子动力学模拟表明扩散离子伴随着F~-亚晶格变形,而Kaneko和Ueda的分子动力学模拟则表明扩散离子伴随着近邻离子在同一运动方向的相关运动。进一步的研究尚待进行。八十年代初,Nelson等人提出了描述晶体、非晶和液态中键取向的键球谐函数方法。 相似文献
957.
Carolina A. Pinto P. M. Büchler J. Dweck 《Journal of Thermal Analysis and Calorimetry》2007,87(3):715-720
The catalyst
used in fluidized catalytic cracking (FCC) units of refineries after several
recovery cycles in regeneration units, reduces its activity and it is partially
substituted by new catalyst in the process. As it has a high silicon and aluminum
oxides content, the pozzolanic properties of a Brazilian FCC spent residual
catalyst, used in different substitution degrees to cement, were evaluated
by three thermal analysis techniques during the early stages of hydration
of a type II Portland cement. NCDTA curves show in real time that the residual
catalyst, accelerates the stages of cement hydration. TG and DSC curves of
respective pastes after 24 h of hydration evidence the pozzolanic activity
of the waste, respectively, by the lower water mass loss during the dehydroxylation
of the residual calcium hydroxide and by the lower dehydroxylation endothermal
effect. Within the analyzed period, the higher is the cement substitution
degree, the higher is the pozzolanic activity of the residual catalyst. 相似文献
958.
Mei Y Wu T Xu C Langenbach KJ Elliott JT Vogt BD Beers KL Amis EJ Washburn NR 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12309-12314
A simple yet versatile method was developed to prepare a low-density polymerization initiator gradient, which was combined with surface-initiated atom transfer radical polymerization (ATRP) to produce a well-defined poly(2-hydroxyethyl methacrylate) (HEMA) gradient substrate. A smooth variation in film thickness was measured across the gradient, ranging from 20 A to over 80 A, but we observed a nonmonotonic variation in water contact angle. Fits of X-ray reflectivity profiles suggested that at the low graft density end, the polymer chain structure was in a "mushroom" regime, while the polymer chains at high graft density were in a "brush" regime. It was found that the "mushroom" region of the gradient could be made adhesive to cells by adsorbing adhesion proteins, and cell adhesion could be tuned by controlling the density of the polymer grafts. Fibroblasts were seeded on gradients precoated with fibronectin to test cellular responses to this novel substrate, but it was found that cell adhesion did not follow the expected trend; instead, saturated cell adhesion and spreading was found at the low grafting density region. 相似文献
959.
Changlun Chen Di Xu Xiaoli Tan Xiangke Wang 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):227-233
The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions.
The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In
this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations
on the Co(II) sorption on γ-Al2O3 in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al2O3 in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed
that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition
orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated
that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly
positive influence of HA at low pH on the Co(II) sorption on γ-Al2O3 was attributed to strong surface binding of HA on γ-Al2O3 and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO−)
x
Co2−x
. Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al2O3 in the presence of HA. 相似文献
960.
A silica monomer-estrone complex (EstSi) having a thermally cleavable urethane bond and a cross-linkable triethoxysilane group was synthesized. From EstSi and TEOS, spherical silica particles with sizes of 1.5-3 mum were prepared. The template molecules were removed from the silica matrix by heating at 180 degrees C in DMSO in the presence of water, generating a cavity with an amino group. The control silica particles that had the same sizes and shapes were obtained with aminopropyl triethoxysilane and TEOS. When ethylene glycol was added in place of H2O, an ethyl alcoholic group was formed in the cavity. Their recognition ability and specific binding for estrone were characterized by uptake experiments. The estrone-imprinted silica particles showed a much higher recognition ability than the control silica particles and higher selectivity for estrone than testosterone propionate. 相似文献