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21.
A method for quantitative measurement of the photochemical decomposition of the anti-inflammatory agent, indoprofen (INP) is descriped. An RPLC-based assay that could determine the extent of degradation of INP in a rapid, sensitive, and accurate manner was developed. The method was validated under photoirradiation. Quantitation was monitored with an Inertsil ODS-3V column using a mobile phase of acetonitril and 1% HOAc solution in deionized H2O. Statistics relevant to the system criteria, peak integrity and resolution among the parent drug and its degradation products were performed. From the intra- and inter-day tests, the coefficients of variation were found to range from 0.59% to 4.25% for the former and from 0.71% to 4.86% for the latter. The good selectivity and specificity of this RPLC-based procedure render it suitable for measurements of INP stability. 相似文献
22.
A SPME-HPLC-post-column fluorescent derivatization method for the direct determination of saxitoxin (STX), the most potent paralytic shellfish poisoning (PSP) toxin, in water has been developed. Commercially available SPME devices with 50 microm Carbowax templated resin (CW/TPR) coating was found to be able to pre-concentrate STX from aqueous media. A special pre-conditioning treatment of soaking the SPME coating in 0.1 M NaOH solution significantly improved the extraction efficiency. The optimal pH for the SPME process is 8.1 and the equilibration time is 40 min. The partition coefficient, K, of the distribution of STX between the SPME coating and the aqueous media was measured to be 2.99 +/- 0.04 x 10(3). Extracted toxin on the SPME stationary phase was difficult to be desorbed by the HPLC mobile phase under dynamic desorption mode. A static ion-pairing desorption technique using a desorption solvent mixture of 20 mM sodium 1-heptanesulfonate in 30% aqueous acetonitrile acidified with 50 mM sulfuric acid was developed to overcome this problem. The method detection limit and repeatability achieved by this SPME-HPLC method were 0.11 ng ml(-1) and 3.7%, respectively, with a sample volume of just 5 ml of water. This analytical method is adequate for the monitoring of the PSP toxin in fresh/drinking waters. However, serious interference was observed when this technique was applied to saline water samples. This is probably due to competition of sodium ions with the cationic STX for absorption into the SPME stationary phase. 相似文献
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Abstract— In dimethylsulfoxide the emission spectrum of luminol chemiluminescence is red-shifted by 300 cm-1 from the photoexcited fluorescence of the product 3-aminophthalate dianion, while in aqueous solvent the two spectra are identical. The spectral properties of the product dianion have been measured in aqueous solvent and in a number of aprotic solvents, both at room temperature and at 77°K. The ground states and the excited states from which emissions are observed are characterized. Two alternatives are presented to explain the aprotic emission spectra. 相似文献
25.
Mulder FA Hon B Mittermaier A Dahlquist FW Kay LE 《Journal of the American Chemical Society》2002,124(7):1443-1451
Recently developed carbon transverse relaxation dispersion experiments (Skrynnikov, N. R.; et al. J. Am. Chem. Soc. 2001, 123, 4556-4566) were applied to the study of millisecond to microsecond time scale motions in a cavity mutant of T4 lysozyme (L99A) using methyl groups as probes of dynamics. Protein expressed in E. coli cells with (13)CH(3)-pyruvate as the sole carbon source contained high levels of (13)C enrichment at a total of 80 Val gamma, Leu delta, Ile gamma (2), Ala beta, and Met epsilon methyl positions with little extraneous incorporation. Data for 72 methyl groups were available for analysis. Dispersion profiles with large amplitudes were measured for many of these residues and were well fit to a two-state exchange model. The interconversion rates and populations of the states, obtained from fitting relaxation dispersion profiles of each individual probe, were remarkably homogeneous and data for nearly all methyl groups in the protein could be collectively fit to a single cooperative conformational transition. The present study demonstrates the general applicability of methyl relaxation dispersion measurements for the investigation of millisecond time scale protein motions at a large number of side-chain positions. Potential artifacts associated with the experiments are described and methods to minimize their effects presented. These experiments should be particularly well suited for probing dynamics in high molecular weight systems due to the favorable NMR spectroscopic properties of methyl groups. 相似文献
26.
We prove that the constant maps are the onlyp-harmonic maps for anyp 2 from an arbitrary compact Riemannian manifold into a complete Riemannian manifold which admits a strictly convex function. 相似文献
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An acoustic technique developed earlier was applied to measure the molar number of fragments produced in the XeCl-laser-induced gas-phase photolysis of Cr(CO)6 and Mo(CO)6. The bluish-green Cr and Mo emissions were also monitored and correlated with the acoustic signal. For laser fluence ranging up to about 25 mJ/cm2 (38 mJ/cm2), the Cr (Mo) optical signal varied with laser fluence asy =dx
3, in agreement with the model that highly excited metal atoms were produced by direct three-photon processes. The acoustic signal varied with fluence asy = ax + bx
2, consistent with the model that most fragments were formed via sequential and direct two-photon processes. Quite expectedly, all coefficientsa,b andd vary linearly with carbonyl partial pressure. Both optical and acoustic signals showed onset of saturation at 25 mJ/cm2 (38 mJ/cm2) for the case of chromium (molybdenum) hexacarbonyl, suggesting that all photolysis channels were equally affected by the depletion of parent molecules. By assuming a common depletion mechanism, upper limits on the branching ratios of the various photolysis channels were estimated. 相似文献
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