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991.
The fabrication of a novel sheathless interface for capillary electrophoresis–electrospray–mass spectrometry (CE–ESI–MS) is described. A programmable CO2 laser was used to ablate small channels in the walls of a polyimide capillary near the terminus. Subsequent exposure of the channel region to a cellulose acetate solution followed by drying resulted in the formation of an electrically conductive semi-permeable membrane. Application of an appropriate voltage to the reservoir resulted in the simultaneous establishment of an electrical connection for CE and ESI. Interface viability was demonstrated by conducting a CE separation of a peptide mixture, with detection accomplished via positive ion mode ESI–MS. For the peptide Val-Tyr-Val, a limit of detection of 0.1 femtomole (S/N 3) was achieved using single reaction monitoring. Attributes of the interface include structural robustness, ease of fabrication, minimal interface dead volume, and the ability to alter post-separation analyte ionization status by use of appropriate buffers in the interface reservoir. 相似文献
992.
A sensitive and accurate LC method was developed and further validated for the determination of enantiomeric purity of GSK962040. Before separation, a pre-column derivatization procedure was performed. Baseline separation with a resolution higher than 1.9 was accomplished within 15 min using a Chiralpak AD-H (250 × 4.6 mm; particle size 5 μm) column, with n-hexane: 2-propanol (85:15 v/v) as mobile phase at a flow rate of 1 mL min?1. The eluted analytes were subsequently detected with a UV detector at 260 nm. The effects of mobile phase components and temperature on enantiomeric selectivity as well as resolution of enantiomers were thoroughly investigated. The calibration curves were plotted within the concentration range between 4 and 200 μg mL?1 (n = 8), and recoveries between 98.15 and 101.48% were obtained, with relative standard deviation (RSD) lower than 1.42%. The LOD and LOQ for the Boc-GSK962040 were 1.23 and 4.15 μg mL?1 and for its enantiomer were 1.38 and 4.76 μg mL?1, respectively. The developed method was also evaluated and validated by analyzing bulk samples with different enantiomeric ratios of GSK962040. It was demonstrated that the method was accurate, robust and sensitive, and also had practical utilities for real analysis. 相似文献
993.
The presentation, development and analysis of a new two-stages tenth algebraic order symmetric six-step method is introduced, for the first time in the literature, in this paper. More specifically, we present the development of the new method (requesting the highest algebraic order and the elimination of the phase-lag and its first and second derivatives), the analysis (error analysis and stability and interval of periodicity analysis) and the evaluation of the new developed method comparing its efficiency with the efficiency of well known methods and very recently produced methods in the literature on the approximate solution of the resonance problem of the one dimensional (or radial) Schrödinger equation. From the developments achieved and the results presented, we prove that the new obtained method is most more effective than other well known or recently developed methods of the literature. 相似文献
994.
Chemical oscillation is an interesting nonlinear dynamical phenomenon which arises due to complex stability condition of the steady state of a reaction far away from equilibrium which is usually characterised by a periodic attractor or a limit cycle around an interior stationary point. In this context Lienard equation is specifically used in the study of nonlinear dynamical properties of an open system which can be utilized to obtain the condition of limit cycle. In conjunction with the property of limit cycle oscillation, here we have shown the condition for isochronicity for different chemical oscillators with the help of renormalisation group method with multiple time scale analysis from a Lienard system. When two variable open system of equations are transformed into a Lienard system of equation the condition for limit cycle and isochronicity can be stated in a unified way. For any such nonlinear oscillator we have shown the route of a dynamical transformation of a limit cycle oscillation to a periodic orbit of centre type depending on the parameters of the system. 相似文献
995.
Yanlou Wang Tiantian Meng Dongdong Jia Yongyue Sun Naixuan Li 《Journal of solution chemistry》2017,46(1):70-88
Solubilities of two calcium channel blockers, nifedipine and lacidipine, were measured in supercritical carbon dioxide at T = (313, 323, and 333) K over the pressure range (12.0–36.0) MPa using a dynamic-analytical apparatus. The solubility values obtained are in the range of (0.18–7.05) × 10?5 mol·mol?1. The solubilities of the two solids show similar trends with a crossover region of the respective isotherms in the range 18.0–21.0 MPa. The experimental solubility data were correlated with several different models. The semi-empirical density-based models provided satisfactory correlation results with AARD values lower than 10%. According to the results of the Méndez-Santiago and Teja models, the measured solid solubility data are quite consistent at all experimental conditions, which indicates the reliability of the data. The compressed gas model of the Peng–Robinson equation of state, combined with the two parameter van der Waals mixing rule (PR-EoS-VDW2) model, gives better correlation results than the PR-EoS-VDW1 model. The expanded liquid model based on Scatchard–Hildebrand regular solution theory can be used for solubility prediction, but the correlation results for nifedipine and lacidipine by the model are inferior to the compressed gas models in this work. 相似文献
996.
Aqueous two phase systems (ATPS), consisting of two incompatible aqueous solutions, are widely used in biological extraction. In recent years, many experimental studies on the phase behavior of ionic liquid(IL)–inorganic salt ATPS systems have been reported but few investigations of the thermodynamics of the IL-based ATPS have been reported. In this work, the Extended UNIQUAC model is modified to calculate the equilibrium of [Bmim]Cl–K2HPO4–H2O ATPS at 298.15 K. All the interaction parameters of the model are salt specific. The results show that the experimental compositions of tie lines are correlated successfully using the proposed model. The root mean square deviation of the mass fraction is 0.0256. 相似文献
997.
Temperature dependent molar conductances and fluidities of bisulfate and ethyl sulfate anion-based ionic liquids were measured. The extent of dissociation of the ionic liquids was estimated from the Walden plot in term of ionicity. The ionicity mainly depends on the magnitude of Coulombic forces, altered by the anion’s Lewis basicity. Aqueous solutions of aprotic ionic liquids, in general, possesses ionicity in the range of ≈70–99%. This article reveals that the substitution of the anion by bisulfate and ethylsulfate reduces the ionicity of aqueous solution of these ionic liquids to the range of 10–37%. This is very close to that exhibited by some of the protic ionic liquids and phosphonium based ionic liquids with sweetner anions. The concentration dependent molar conductance of these ionic liquids has been fitted to Mahiuddin and Ismail’s equation. To our surprise, the molar conductances of bisulfate-based aprotic ionic liquids are remarkably high, even though these ionic liquids possess lower ionicity. 相似文献
998.
W. Earle Waghorne 《Journal of solution chemistry》2017,46(9-10):1818-1835
A theorem presented by Professor Ben-Naim (J Phys Chem 82:874–885, 1978) states that the standard state enthalpy and entropy changes arising from changes in the solvent structure that are induced by solvation of a solute cancel exactly in the standard state Gibbs energy. In this paper this is explored by consideration of the thermodynamics of transfer of electrolytes in mixed solvents, using previously developed models of the solvation process. Two cases are considered. One is random solvation, where curvatures in plots of the transfer enthalpies and entropies, which arise from changes in solvent–solvent interactions, exactly compensate in the transfer Gibbs (free) energies, which are sensibly linear with solvent composition. The second type of system are those with strong preferential solvation where it is found that the transfer Gibbs energies can be accounted for quantitatively in terms of changes in the solute–solvent interactions, with no contribution from changes in solvent–solvent interactions. The results are entirely consistent with the Ben-Naim theorem. 相似文献
999.
Olga N. Pestova Andrey Yu. Efimov Lyubov A. Myund Andrei G. Kudrev Vasiliy D. Khripun Anna G. Davidian Valeria E. Baranauskaite 《Journal of solution chemistry》2017,46(9-10):1854-1870
A new approach has been proposed to study the structure of aqueous electrolyte solutions. NIR, Raman and attenuated total reflectance, Fourier transform infra-red (ATR FTIR) spectra have been measured for aqueous calcium perchlorate solutions in the 0.22–4.3 mol·L?1 (0.22–7.46 mol·kg?1) concentration range at 25 °C. By the methods of principal component analysis (PCA) and multivariate curve resolution—alternating least squares (MCR-ALS) the number, spectra and concentration profiles have been determined for spectroscopically distinguishable forms of water and ClO 4 ? ion in solutions. The results have been analyzed using a phenomenological model, establishing thereby: concentration ranges for structural rearrangements of the solution, the nature of structural microirregularities and different states of the ClO 4 ? ion in the areas of domination of the natural water structure, and of cybotactic groups of calcium perchlorate hexa and tetra hydrates. 相似文献
1000.
Nirvik Sen K. Saswani K. K. Singh S. Barkade S. Mukhopadhyay S. M. Chavan Sk. M. Ali K. T. Shenoy 《Journal of Radioanalytical and Nuclear Chemistry》2017,312(2):255-262
Batch extraction of uranium(VI) from uranyl nitrate solutions using TiAP in ionic liquids ([BMIM]PF6 and [HMIM]PF6) is studied. Effects of acidity, TiAP concentration in ionic liquid and temperature on distribution coefficient are studied. Results show that distribution coefficient increases with an increase in acidity and reduces with an increase in the alkyl chain length of the cation of the ionic liquid. Extraction of uranium(VI) by TiAP-[HMIM]PF6 system is found to involve two molecules of the extractant per metal ion and extraction is found to change from being exothermic to endothermic as the percentage of the extractant is increased. 相似文献