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991.
Heaton J Whiley L Hong Y Sebastian CM Smith NW Legido-Quigley C 《Journal of separation science》2011,34(10):1111-1115
Aristolochic acids are known to contribute to various renal disorders; therefore, expanding the availability of analytical methodology to detect these compounds is important in order to assess the quality of Chinese herbal medicines in which they can be found. Twelve medicinal herbal samples were procured from various sources and extracted in duplicate prior to a "fingerprint" analysis using conventional HPLC-DAD. Multivariate analysis was performed on the entire chromatographed fingerprints. The resulting output was a partial least-square discriminant analysis model, which was able to evaluate the potential presence of aristolochic acids I and II as well as providing an individual herbal "fingerprint". The results of this study provide evidence that the presence of aristolochic acids contained within certain herbal extractions could be detected using a simple method, although some limitations apply to this method for quality control, since newly detected samples for aristolochic acid (positives) will need further confirmation with purity checks or MS hyphenation. 相似文献
992.
We derive a statistical mechanical model for colloidal interactions mediated by polymer-like micelles (PLMs) that adsorb at the colloid surface. The model considers the end-adsorption and reversible scission of ideal chains, and is based on experimentally measurable parameters relevant to PLMs. The model predicts interparticle attractions due to micellar bridging that are stronger and longer-range than those encountered in ordinary telechelic polymers. Mapping the analytical potential onto the more familiar Double Yukawa potential allows, for the first time, accurate, a priori prediction of suspension microstructure and phase behavior when compared to experimental data for model nanoparticles dispersed in wormlike micelles over a range of solution conditions. 相似文献
993.
We have performed relativistic calculations of single and double core 1s hole states of the noble gas atoms in order to explore the relativistic corrections and their additivity to the ionization potentials. Our study unravels the interplay of progression of relaxation, dominating in the single and double ionization potentials of the light elements, versus relativistic one-electron effects and quantum electrodynamic effects, which dominate toward the heavy end. The degree of direct relative additivity of the relativistic corrections for the single electron ionization potentials to the double electron ionization potentials is found to gradually improve toward the heavy elements. The Dirac-Coulomb Hamiltonian is found to predict a scaling ratio of ~4 for the relaxation induced relativistic energies between double and single ionization. Z-scaling of the computed quantities were obtained by fitting to power law. The effects of nuclear size and form were also investigated and found to be small. The results indicate that accurate predictions of double core hole ionization potentials can now be made for elements across the full periodic table. 相似文献
994.
Hydrophilic interaction chromatography (HILIC) has experienced increasing attention in recent years. Much research has been carried out in the area of HILIC separation mechanisms, column techniques and applications. Because of their good permeability, low resistance to mass transfer and easy preparation within capillaries, hydrophilic monolithic columns represent a trend among novel HILIC column techniques. This review attempts to present an overview of the preparation and applications of HILIC monolithic columns carried out in the past decade. The separation mechanism of various hydrophilic monolithic stationary phases is also reviewed. 相似文献
995.
Solvent systems for use with LC-MS often result in a compromise between chromatographic performance and mass spectrometric detection, exemplified here by a LC-MS/MS method development for the analysis of ephedrines in doping control. Ephedrines, frequently found in therapeutic and nutritional preparations, are among the most commonly administered doping agents in competitive sport. Improved separation of these hydrophilic, basic compounds, some of which are diastereoisomers, is achieved in reversed-phase LC by the use of a high pH mobile phase in order to suppress analyte ionisation, and thus alter their polarity, resulting in reduced peak tailing and enhanced retention. However, when coupled to an ESI-MS detector, this eluent composition generated a non-linear and poorly reproducible signal. APCI yielded greater stability and reproducibility and is here presented as an ion source for the analysis of basic compounds under conditions that suppress their ionisation. Errors as large as 49.3% were observed with ESI, compared with 15.4% generated using APCI, for pseudoephedrine over the calibration range (25-400 μg/mL) in urine with a simple dilution and injection of samples. These data highlight the importance of suitable MS conditions for stable performance, necessary for accurate quantification, without undue compromise to the LC separation. 相似文献
996.
Kinetics and mechanism of photoprocesses generated by visible light-irradiation of the system riboflavin (Rf, vitamin B2) plus Thiamine (Th) and Thiamine pyrophosphate (ThDP), representing vitamin B1, was studied in pH 7 water. A weak dark complex vitamin B2-vitamin B1, with a mean value of 4 ± 0.4 M(-1) is formed. An intricate mechanism of competitive reactions operates upon photoirradiation, being the light only absorbed by Rf. Th and ThDP quench excited singlet and triplet states of Rf, with rate constants in the order of 10(9) and 10(6 ) M(-1 ) s(-1), respectively. With Vitamin B1 in a concentration similar to that of dissolved molecular oxygen in water, the quenching of triplet excited Rf by the latter is highly predominant, resulting in the generation of O(2)((1)Δ(g)). Superoxide radical anion was not detected under work conditions. A relatively slow O(2)((1)Δ(g))-mediated photodegradation of Th and ThDP was observed. Nevertheless, Th and especially ThDP behave as efficient physical deactivators of O(2)((1)Δ(g)). The thiazol structure in vitamin B1 appears as a good scavenger of this reactive oxygen species. This characteristic, that presents at vitamin B1 as a potential photoprotector of biological entities against O(2)((1)Δ(g)) attack, was been experimentally confirmed employing the protein lisozime as a photo-oxidizable target. 相似文献
997.
A theory for the dielectric constant, ε, of a fluid mixture of dipolar hard spheres is formulated by generalizing the methods developed by Ramshaw and Wertheim for the pure fluid case. The resulting expression for ε depends on the pair distribution functions, g αβ(r 1, θ1, r 2, θ2) for a dipolar mixture. Due to the unavailability of exact representations for these dipolar pair distribution functions, the results of the mean spherical approximation are employed in the formalism developed. Numerical results are given for ε as calculated from the pair distribution functions for a spherical volume of macroscopic dimensions. The compositional dependence of the ε obtained in this way for a specific mixture is compared with the corresponding properties of the well established theories of Clausius-Mossotti-Debye and Onsager. In addition, the relative importance of the dipole moment and size of the hard sphere parameters in determining ε for a dipolar mixture (the correlative behaviour of which is described by the mean spherical approximation) is evaluated. It is found that the differences in hard core diameters can be largely ignored, in that ε for an ‘effective’ single component fluid can be given to within 2–5 per cent relative error (at worst) of the mean spherical approximation's result. Such an ‘effective pure fluid’ is described as having the same polarization content as the actual mixture being considered. Thereby, the properties of the effective fluid are determined by the quantity y = 4πβ(m 1 2 ρ1 + m 2 2 ρ2)/9 where mi and ρ i are the dipole moment and number density of component i in the binary mixture, with β = (kT)-1. 相似文献
998.
The general formula for the number of diagrammatic terms occurring in the Tn equation within a particular coupled cluster model is derived. Both the antisymmetrized and Goldstone diagrams are considered. In addition to the full coupled cluster equation approximate approaches are discussed, and for each the general formula for the number of terms is given. Analogous expressions are presented for the number of diagrammatic terms contributing to the elements of the transformed Hamiltonian [Hbar] = e?T HeT . 相似文献
999.
Norman McCubbin 《Contemporary Physics》2013,54(4):319-333
1000.