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61.
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63.
A method for preparation of capillary columns and traps with a very thick film (up to 100 μm) of stationary phase is described. The principle of this method is based on an immediate fixation of a film of prepolymer, formed during dynamic coating. Thus, the development of film irregularities, such as are caused by Rayleigh instability is avoided. Fixation of the film is conveniently accomplished by heat-accelerated crosslinking as was demonstrated in this work, where a commercially available silicone prepolymer (Sylgard 184, Dow Corning) was employed. The low phase ratio columns which thus can be prepared are interesting both in chromatography with dense mobile phases and as enrichment devices. Examples of the latter application are shown, where trace organic components from air and water were concentrated. 相似文献
64.
A polyacrylate/polyurethane (P(A) / P(U)) composite coating has been prepared bycrosslinking an acetoacetylated polyacrylate with a vinylic group terminated polyurethaneat room temperature. A model Michael reaction between ethyl acetoacetate (EAA) andmethyl acrylate (MA) was designed to study the crosslinking mechanism. It was foundthat the two active hydrogen atoms in acetoacetyl group can both add to vinylic groupsand the yield of mono- and bis-adducts are much affected by the molar ratio of acetoacetylto vinylic groups. Higher crosslinking degree and better properties could be obtained withdecreasing the molar ratio of the two active groups from 1/1 to 0.6/1 in the compositecoatings. 相似文献
65.
A titanium dioxide sol with narrow particle size distribution was synthesized using TiCl4 as the starting material. The sol was prepared by a process where HCl was added to a gel of hydrated titanium oxide to dissolve it. The resulting aqueous titanic acid solution was heated to form titanium dioxide sol. The effects of preparation parameters were investigated. TiCl4 was slowly added to distilled water at 5°C. Aqueous solution of sodium hydroxide was added to adjust the pH of the system to 8–12. After aging for a period of time, the peptized sol was filtered and sufficiently washed. The filtered cake was repulped in water. Hydrochloric acid was slowly added to the solution with stirring. After condensation reaction and crystallization, a transparent sol with suspended TiO2 was formed. XRD results show that the crystalline phase was anatase. The suspended TiO2 particles were rhombus primary particles with the major axis ca. 20 nm and the minor axis ca. 5 nm. The TiO2 particles prepared at pH 8 had the largest surface area of 141 cm3/g and it was microporous. The compositions of the solution which yielded the smallest suspended TiO2 particles were TiO2:HCl (35% HCl) = 1:1 (molar ratio), concentration of TiO2 = 10%. Hydroxypropyl cellulose with viscosity of 150–400 cps was added as a dispersant. The sol was excellent in dispersibility and long-term stability. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The dip-coating on glass can be less than three times to have one monolayer TiO2. The transparent TiO2 thin film had strong hydrophilicity after being illuminated by UV light. 相似文献
66.
Ting-Fu Jiang 《Analytica chimica acta》2003,479(2):249-254
Ionic substances with melting points close to room temperature are referred to as ionic liquids. Because ionic liquids are environmentally benign and are good solvents for a wide range of both organic and inorganic materials, interest for their potential uses in different chemical processes is increasing. In this paper, a capillary electrophoretic method for the analysis of basic proteins including lysozyme, cytochrome c, trypsinoge, and α-chymotyypsinogen A is reported. The method, in which 1-alkyl-3-methylimidazolium-based ionic liquids are used as the running electrolytes, leads to a surface charge reversal on the capillary wall. The effects of the alkyl group, imidazolium counterion, and the concentration of the ionic liquids were discussed. The optimum buffer system was a 90 mM 1-ethyl-3-methylimidazolium tetrafluoroborate (1E-3MI-TFB) solution. The applied voltage was −15 kV and detection was performed by monitoring absorbance at 240 nm. Baseline separation, high efficiencies, and symmetrical peaks of four proteins were obtained. The R.S.D. values of migration times and peak areas were <0.68 and <3.0%, respectively. The separation mechanism seems to involve association between the imidazolium cations and the proteins. 相似文献
67.
Ostanina T. N. Rudoi V. M. Yaroslavtseva O. V. Solov'ev A. S. Subbotina O. Yu. Dokashenko S. I. 《Russian Journal of Electrochemistry》2004,40(10):1019-1023
The impedance of zinc-rich polymer coatings on steel in a 3-% NaCl solution is studied. The electrochemical behavior of the electrode is satisfactorily described by an equivalent circuit that contains a constant-phase element, which reflects fractal properties of the zinc surface in the binder. From the results of calculations of the circuit elements for metal-rich electrodes with different zinc contents computed are fractions of the active area of the surface of the coating and its fractal dimensionality. 相似文献
68.
Martin Gilges Heribert Husmann Maria-Helen Kleemiß Stephan R. Motsch Gerhard Schomburg 《Journal of separation science》1992,15(7):452-457
Mixtures of several basic proteins have been used to test CZE capillaries with surfaces modified by new pretreatment procedures; the performance obtained has been compared with that achieved using capillaries treated by procedures described in the literature. It has been shown that addition of non-ionic polyvinylalcohols (PVA) to CZE buffer solutions deactivates even bare, i.e. untreated, fused silica surfaces and renders them suitable for separations of basic proteins. The performance obtained from such surfaces was comparable with that of capillaries modified by the more elaborate procedures of etching, silanol derivatization, and/or adsorptive coating (again with polymers). A home-made device is described which enables derivatization and coating reactions to be performed on fused silica capillaries under an inert atmosphere, i.e. one free from oxygen and water. 相似文献
69.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
70.
In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h?1) has been achieved. 相似文献