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991.
992.
Capillary electrophoresis with wavelength-resolved laser-induced fluorescence detection 总被引:5,自引:0,他引:5
Capillary electrophoresis (CE) enables rapid separations with high separation efficiency and compatibility with small sample volumes. Laser-induced fluorescence detection can result in extremely low limits of detection in CE. Single-channel fluorescence detection, however, furnishes little qualitative information about a species being detected, except for its CE migration time. Use of multidimensional information often enables unambiguous identification of analytes. Combination of CE with information-rich wavelength-resolved fluorescence detection is analogous with ultraviolet-visible diode-array detection and furnishes both qualitative and quantitative chemical information about target species. This review discusses recent advances in wavelength-resolved laser-induced fluorescence detection coupled with CE, with an emphasis on instrument design. 相似文献
993.
A type of high visible-light active titanium oxinitride(TiO2-xNx) powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures. The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white. The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied. The visible-light activity and photocatalysis capability of the powder were also investigated. 相似文献
994.
Samuel González-Mancebo Javier Lacadena Yolanda García-Alonso Jesús Hernández-Benito Emilio Calle Julio Casado 《Monatshefte für Chemie / Chemical Monthly》2002,133(2):157-166
Summary. Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of
the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction
was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO+/NO2H2
+ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron
donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly
by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.
Received July 13, 2001. Accepted (revised) September 18, 2001 相似文献
995.
(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric
acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures
of the ligand and its complexes have been established by i. r., 1H- and 13C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements. 相似文献
996.
Lehmler HJ Rama Rao VV Nauduri D Vargo JD Parkin S 《Journal of fluorine chemistry》2007,128(6):595-607
Alkylated perfluorooctanesulfonamides are compounds of environmental concern. To make these compounds available for environmental and toxicological studies, a series of N-alkylated perfluorooctanesulfonamides and structurally related compounds were synthesized by reaction of the corresponding perfluoroalkanesulfonyl fluoride with a suitable primary or secondary amine. Perfluoroalkanesulfonamidoethanols were obtained from the N-alkyl perfluoroalkanesulfonamides either by direct alkylation with bromoethanol or alkylation with acetic acid 2-bromo-ethyl ester followed by hydrolysis of the acetate. N-Alkyl perfluorooctanesulfonamidoacetates were synthesized in an analogous way by alkylation of N-alkyl perfluoroalkanesulfonamides with a bromo acetic acid ester, followed by basic ester hydrolysis. Alternatively, N-alkyl perfluoroalkanesulfonamides can be alkylated with an appropriate alcohol using the Mitsunobu reaction. Perfluorooctanesulfonamide was synthesized from the perfluorooctanesulfonyl fluoride via the azide by reduction with Zn/HCl. All perfluorooctanesulfonamides contained linear as well as branched C8F17 isomers, typically in a 10:1 to 30:1 ratio. The crystal structures of N-ethyl and N,N-diethyl perfluorooctanesulfonamide show that the S-N bond has considerable double bond character. This double bond character results in a significant rotational barrier around the S-N bond (ΔG≠ = 62-71 kJ mol−1) and a preferred solid state and solution conformation in which the N-alkyl groups are oriented opposite to the perfluorooctyl group to minimize steric crowding around the S-N bond. 相似文献
997.
Previous work on the electrochemistry of palladium in aqueous acid solution demonstrated the existence of two multilayer
hydrous oxide reduction peaks, one at ca. 0.24 V and another at ca. 0.55 V vs. RHE, plus the presence of a reversible active
surface state transition at ca. 0.24 V. In the present work with thermally activated palladium it was observed that, in agreement
with the hydrous oxide reduction behaviour of the system, there is a second active state transition at E≥ca. 0.45 V. In most of its reactions in aqueous acid solution, apart from its unusual capacity to absorb hydrogen, palladium
exhibits properties very similar to those of platinum; however, palladium seems to be more prone to dissolution and subsurface
oxygen formation. Also the premonolayer oxidation responses of these two metals are often different as the more active state
of the palladium surface is not as readily generated as that of platinum. The electrocatalytic properties of palladium, as
reported earlier, correlate quite well with the hydrous oxide and premonolayer oxidation behaviour of this electrode system.
Electronic Publication 相似文献
998.
Transition metal (TM) hydrides display a remarkable range of bonding types, encompassing classical M-H moieties, dihydrogen complexes containing the eta 2-H2 ligand, and trihydrides which display quantum mechanical site exchange. Furthermore, C-H, Si-H and B-H moieties can bind to TM centres in an eta 2-manner, to give sigma-bond complexes with a spectrum of M...H contributions. In addition to these primary bonding modes, TM complexes also indulge in a wide spectrum of hydrogen-bonding interactions, including both M...H-X and the unique type M-H...H-X. This review begins with a historical perspective of the development of TM hydride chemistry, and proceeds to focus on three significant developments of the past two decades: the discovery of sigma-bond and dihydrogen complexes, the involvement of TM hydrides in hydrogen bonding, and the role played by quantum mechanical phenomena in the chemistry and dynamics of TM hydrides. The account concludes with an overview of the inter-relationship between these apparently disparate novel aspects of TM hydride chemistry. 相似文献
999.
Inmaculada Escorihuela Larry R. Falvello Milagros Tomás 《Journal of Cluster Science》2004,15(4):425-435
The reaction of the tetranuclear cyanide aquo complex [{Pt(CN)4Cu(bipy)(H2O)}2]· 2H2O with aqueous ammonia produces the new tetranuclear ammino-containing product [{Pt(CN)4Cu(bipy)(NH3)}2] (1), with terminal cyanide groups and with NH3 coordinated to the Cu atom. The distorted trigonal bipyramidal coordination about copper in 1 differs from the square-pyramidal coordination present in the starting material. The bipyridine ligand in 1 is nearly perpendicular to the tetranuclear core of the molecule, as opposed to its coplanar disposition in the aquo complex. The two platinum atoms of the tetranuclear core in 1 form Pt···Pt interactions of 3. 2390(8) Å with platinum atoms of neighboring molecules, producing an echelon-shaped supramolecular chain held together by staggered (CN)4Pt···Pt(CN)4 linkages, an aggregate structure which does not have a precedent in chemistry derived from the Pt(CN)4 building block. 相似文献
1000.
Katalin Mészáros Szécsényi I. Esztelecki G. Pokol 《Journal of Thermal Analysis and Calorimetry》2007,89(3):829-833
In order to increase the nutrition value of bread, one of the most commonly used foodstuff all over the world, different additives
are used in bread processing. In this paper we describe the thermal changes in bread and that of with 0.5% crude soybean lecithin
additive. Their thermal stability has been investigated by TG, DSC and EGD methods. The thermal changes were also followed
of soy products, lecithin and lysine, ingredients used as bread additives in order to check if they may suffer any thermal
degradation during the baking process. The data obtained can be of use only for qualitative conclusions. According to the
obtained data at the usual bread baking temperature only the additives in crust may partly decompose while in the crumb, at
lower temperatures the additives, due to baking, are not damaged. The thermal methods give a possibility for rapid estimation
of processes induced by heat effects in additives during the baking, and they are suitable to detect the changes during the
bread-making procedure. However, they are neither suitable to provide any quantitative data on these changes nor facts affecting
the nutrition value and of the bread. 相似文献