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991.
The double bond migration of butene catalyzed by 1-ethyl-3-methyl-imidazolium fluoride (EmimF) has been studied using quantum chemical method. The geometries of reactant, transition state and product for the isomerization have been optimized by density functional theory (DFT) at the B3PW91/6-31G(d,p), 6-311++G(d,p) and aug-cc-PVDZ levels. The computed results show that the 4-H atom on imidazole ring of EmimF has a good catalytic activity to the double bond migration of butene and the catalytic reaction of 1-butene to 2-butene is a synergetic and elementary process. The apparent activation energy of isomerization is about 197 kJ/mol. 相似文献
992.
993.
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995.
Pan F Wang P Lee K Wu A Turro NJ Koberstein JT 《Langmuir : the ACS journal of surfaces and colloids》2005,21(8):3605-3612
We report a simple photolithographic approach for the creation and micropatterning of chemical functionality on polymer surfaces by use of surface-active block copolymers that contain protected photoactive functional groups. The block copolymers self-assemble at the substrate-air interface to generate a surface that is initially hydrophobic with low surface tension but that can be rendered hydrophilic and functional by photodeprotection with UV radiation. The block copolymer employed, poly(styrene-b-tert butyl acrylate), segregates preferentially to the surface of a polystyrene substrate because of the low surface tension of the polyacrylate blocks. The strong adsorption of block copolymers causes a bilayer structure to form presenting a photoactive polyacrylate layer at the surface. In the example described, the tert-butyl ester groups on the polyacrylate blocks are deprotected by exposure to UV radiation in the presence of added photoacid generators to form surface carboxylic acid groups. Surface micropatterns of carboxylic acid groups are generated by UV exposure through a contact mask. The success of surface chemical modification and pattern formation is demonstrated by X-ray photoelectron spectroscopy and contact angle measurements along with imaging by optical and fluorescence microscopy methods. The resultant chemically patterned surfaces are then used to template patterns of various biomolecules by means of selective adsorption, covalent bonding and molecular recognition mechanisms. The surface modification/patterning concept can be applied to virtually any polymeric substrate because protected functional groups have intrinsically low surface tensions, rendering properly designed block copolymers surface active in almost all polymeric substrates. 相似文献
996.
A capillary electrophoresis (CE) method was developed for the separation of heparin oligosaccharides compatible to study the interactions between the oligosaccharides and granulocyte-colony stimulating factor (G-CSF). Unfractionated heparin was eliminitively degraded to heparin oligosaccharides by an endolytic heparinase. The degraded smaller oligosaccharides (M(r) < 1000) were baseline-separated by CE under a 50 mM phosphate buffer (pH 9.0) in 10 min. Standard heparin disaccharides and larger oligosaccharides (1000 < M(r) < 8000) were all separated under optimized separation conditions. Compared with standard heparin disaccharides, smaller oligosaccharides contained one nonsulfated, two monosulfated, and two disulfated disaccharides, but trisulfated disaccharides were not found. The smaller oligosaccharides were also identified and molecular mass was deduced by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, interactions between G-CSF and the oligosaccharides were studied by using capillary zone electrophoresis (CZE) under the above separation conditions. It was found that larger oligosaccharides could interact with G-CSF while smaller oligosaccharides were not observed to bind to G-CSF under the experimental conditions. In conclusion, the purified heparinase could selectively degrade heparin into oligosaccharides and the interaction between G-CSF and heparin was correlated with the chain length of heparin. 相似文献
997.
Synchrotron-based in situ time-resolved x-ray diffraction and x-ray absorption spectroscopies were used to study the behavior of nanostructured {Au+AuO(x)}-CeO(2) catalysts under the water-gas shift (WGS) reaction. At temperatures above 250 degrees C, a complete AuO(x)-->Au transformation was observed with high catalytic activity. Photoemission results for the oxidation and reduction of Au nanoparticles supported on rough ceria films or a CeO(2)(111) single crystal corroborate that cationic Au(delta+) species cannot be the key sites responsible for the WGS activity at high temperatures. The rate determining steps for the WGS seem to occur at the gold-ceria interface, with the active sites involving small gold clusters (<2 nm) and O vacancies. 相似文献
998.
YUAN Liwei WANG Yanqiu WANG Li BAI Jiling & HE Guozhong State Key Laboratory of Molecular Reaction Dynamics Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian China 《中国科学B辑(英文版)》2004,47(4)
Dichlorobenzene is a precursor molecule of di-oxins, which are some of the most toxic chemicals and are suspected of being mutagenic with the structure of benzene rings containing different numbers of chlorine atoms. They are seriously harmful to the health of human. Therefore, it is necessary to study these aryl chemicals especially dichlorobenzene molecules in great detail. In recent years, a number of groups have investi-gated the molecules of aryl halide. The near ultraviolet absorption sp… 相似文献
999.
1000.
Khenkin AM Weiner L Wang Y Neumann R 《Journal of the American Chemical Society》2001,123(35):8531-8542
The mechanism of aerobic oxidation of aromatic and alkyl aromatic compounds using anthracene and xanthene, respectively, as a model compound was investigated using a phosphovanadomolybdate polyoxometalate, H(5)PV(2)Mo(10)O(40), as catalyst under mild, liquid-phase conditions. The polyoxometalate is a soluble analogue of insoluble mixed-metal oxides often used for high-temperature gas-phase heterogeneous oxidation which proceed by a Mars-van Krevelen mechanism. The general purpose of the present investigation was to prove that a Mars-van Krevelen mechanism is possible also in liquid-phase, homogeneous oxidation reactions. First, the oxygen transfer from H(5)PV(2)Mo(10)O(40) to the hydrocarbons was studied using various techniques to show that commonly observed liquid-phase oxidation mechanisms, autoxidation, and oxidative nucleophilic substitution were not occurring in this case. Techniques used included (a) use of (18)O-labeled molecular oxygen, polyoxometalate, and water; (b) carrying out reactions under anaerobic conditions; (c) performing the reaction with an alternative nucleophile (acetate) or under anhydrous conditions; and (d) determination of the reaction stoichiometry. All of the experiments pointed against autoxidation and oxidative nucleophilic substitution and toward a Mars-van Krevelen mechanism. Second, the mode of activation of the hydrocarbon was determined to be by electron transfer, as opposed to hydrogen atom transfer from the hydrocarbon to the polyoxometalate. Kinetic studies showed that an outer-sphere electron transfer was probable with formation of a donor-acceptor complex. Further studies enabled the isolation and observation of intermediates by ESR and NMR spectroscopy. For anthracene, the immediate result of electron transfer, that is formation of an anthracene radical cation and reduced polyoxometalate, was observed by ESR spectroscopy. The ESR spectrum, together with kinetics experiments, including kinetic isotope experiments and (1)H NMR, support a Mars-van Krevelen mechanism in which the rate-determining step is the oxygen-transfer reaction between the polyoxometalate and the intermediate radical cation. Anthraquinone is the only observable reaction product. For xanthene, the radical cation could not be observed. Instead, the initial radical cation undergoes fast additional proton and electron transfer (or hydrogen atom transfer) to yield a stable benzylic cation observable by (1)H NMR. Again, kinetics experiments support the notion of an oxygen-transfer rate-determining step between the xanthenyl cation and the polyoxometalate, with formation of xanthen-9-one as the only product. Schemes summarizing the proposed reaction mechanisms are presented. 相似文献