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71.
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
72.
Robert S. Pomeroy Jeffrey D. Kolczynski Jonathan V. Sweedler M. Bonner Denton 《Mikrochimica acta》1989,99(3-6):347-353
A unique simultaneous emission spectrograph is utilized to perform qualitative and quantitative analysis on trace quantities of solid particulates. The atomic emission spectroscopic system consists of a direct current plasma source and an echelle spectrograph with a charge injection device detector, enabling the system to simultaneously measure the wavelength range from 220 nm to 520 nm with 0.02 nm resolution at 300 nm. Monitoring all wavelengths simultaneously allows the qualitative and quantitative determination of most major and minor constituent in a trace quantity of sample with little prior knowledge about the sample. The ability to perform qualitative and quantitative analysis on particulates is demonstrated by evaluating NBS certified coal fly ash, as well as a sample taken from the respirator air filter at an acute care unit in a hospital.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria 相似文献
73.
Beams of hyperthermal K atoms cross beams of the oriented haloforms CF(3)H, CCl(3)H, and CBr(3)H, and transfer of an electron mainly produces K(+) and the X(-) halide ion which are detected in coincidence. As expected, the steric asymmetry of CCl(3)H and CBr(3)H is very small and the halogen end is more reactive. However, even though there are three potentially reactive centers on each molecule, the F(-) ion yield in CF(3)H is strongly dependent on orientation. At energies close to the threshold for ion-pair formation ( approximately 5.5 eV), H-end attack is more reactive to form F(-). As the energy is increased, the more productive end switches, and F-end attack dominates the reactivity. In CF(3)H near threshold the electron is apparently transferred to the sigma(CH) antibonding orbital, and small signals are observed from electrons and CF(3)(-) ions, indicating "activation" of this orbital. In CCl(3)H and CBr(3)H the steric asymmetry is very small, and signals from free electrons and CX(3)(-) ions are barely detectable, indicating that the sigma(CH) antibonding orbital is not activated. The electron is apparently transferred to the sigma(CX) orbital which is believed to be the LUMO. At very low energies the proximity of the incipient ions probably determines whether salt molecules or ions are formed. 相似文献
74.
Graham Smith Urs D. Wermuth Peter C. Healy Jonathan M. White 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):o203-o207
The structures of two pseudopolymorphic hydrates of brucine, C23H26N2O4·4H2O, (I), and C23H26N2O4·5.25H2O, (II), have been determined at 130 K. In both (I) and (II) (which has two independent brucine molecules together with 10.5 water molecules of solvation in the asymmetric unit), the brucine molecules form head‐to‐tail sheet substructures, which associate with the water molecules in the interstitial cavities through hydrogen‐bonding associations and, together with water–water associations, give three‐dimensional framework structures. 相似文献
75.
A method is described for the preparation of substrate microarrays that allow for the rapid determination of protease substrate specificity. Peptidyl coumarin substrates, synthesized on solid support using standard techniques, are printed onto glass slides using DNA microarraying equipment. The linkage from the peptide to the slide is formed through a chemoselective reaction, resulting in an array of uniformly displayed fluorogenic substrates. The arrays can be treated with proteases to yield substrate specificity profiles. Standard instrumentation for visualization of microarrays can be used to obtain comparisons of the specificity constants for all of the prepared substrates. The utility of these arrays is demonstrated by the selective cleavage of preferred substrates with trypsin, thrombin, and granzyme B, and by assessing the extended substrate specificity of thrombin using a microarray of 361 different peptidyl coumarin substrates. 相似文献
76.
The origins and properties of evaporation and condensation coefficients are described, and results of their measurement are surveyed for water and liquid metals. Contrasts are drawn as to whether their values are likely to limit practical transfer rates at plane surfaces and on aerosols, and between evaporation and condensation. Existing theories which express condensation and evaporation rates in terms of the coefficients are described. Their failure to satisfy energy and momentum conservation as well as mass conservation at the interface is remedied by constructing a new theory which also starts with vapor molecules in Maxwell-Boltzmann distributions. The resulting rates are shown to be close to those predicted by more accurate theories in which the Boltzmann transport equation is solved. 相似文献
77.
Hedstrom JA Toney MF Huang E Kim HC Volksen W Magbitang T Miller RD 《Langmuir : the ACS journal of surfaces and colloids》2004,20(5):1535-1538
Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology. 相似文献
78.
Eric W. Ainscough Tom A. James Stephen D. Robinson Jonathan N. Wingfield 《Journal of organometallic chemistry》1973,60(2):C63-C66
Osmium triphenylphosphine complexes, OsH4(PPh3)3, OsH2 (CO)(PPh3)3 and OsHCl(CO)(PPh3)3 react with triphenyl phosphite in boiling organic solvents to yield triphenyl phosphite derivatives which subsequently undergo ortho-metallation reactions. 相似文献
79.
Boland NA Casey M Hynes SJ Matthews JW Smyth MP 《The Journal of organic chemistry》2002,67(11):3919-3922
A novel procedure for the preparation of enantiopure 1,4-disubstituted 2-imidazolines is reported. Enantiopure beta-amino alcohols are converted into N-hydroxyethylamides, which are reacted with excess thionyl chloride, or with thionyl chloride followed by phosphorus pentachloride to yield N-chloroethylimidoyl chlorides. These intermediates are treated with amines and anilines to produce N-chloroethylamidines, which are converted into imidazolines upon workup with aqueous hydroxide. The method is simple and efficient and has been used to prepare a wide variety of enantiopure imidazolines, in a modular fashion, from readily available amino alcohols. 相似文献
80.
Jonathan B. Ball Margaret G. Wong Benny Capuano Jacqueline M. Gulbis Maureen F. Mackay Paul F. Alewood 《Journal of heterocyclic chemistry》1990,27(2):279-286
The constrained dipeptide mimic 1 was synthesized from 2 in three steps with 65% overall yield. Analyses of the 1H nmr data of a number of 3-amino-2,5-dioxo-2,3,4,5-tetrahydro-1H-1-benzazepine derivatives led to the conclusion that these compounds adopt a similar conformation and that this ring system is rigid. X-ray crystallography was used to define the structure of 3 , and computer-aided energy minimization of 6 gave a preferred conformation similar to that observed in the crystal of 3 . 相似文献