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991.
Le Bihan T Duewel HS Figeys D 《Journal of the American Society for Mass Spectrometry》2003,14(7):719-727
We have developed an on-line strong cation exchange (SCX)-ESI-MS/MS platform for the rapid identification of proteins contained in mixtures. This platform consists of a SCX precolumn followed by a nanoflow SCX column on-line with an electrospray ion trap mass spectrometer. We also used this platform to study the dynamics of peptide separation/extraction by SCX, in particular to understand the parameters affecting the performance of SCX in multidimensional chromatography. For example, we have demonstrated that the buffer typically used for tryptic digestion of protein mixtures can have a detrimental effect on the chromatographic behaviour of peptides during SCX separations, thereby affecting certain peptide quantitation approaches that rely on reproducible peptide fractionation. We have also demonstrated that band broadening results when a step (discontinuous) gradient approach is used to displace peptides from the SCX precolumn, reducing the separation power of SCX in multidimensional chromatography. In contrast, excellent chromatographic peak shapes are observed when a defined (continuous) gradient is used. Finally, using a tryptic digest of a protein extract derived from human K562 cells, we observed that larger molecular weight peptides are identified using this on-line SCX approach compared to the more conventional reverse phase (RP) LC/MS approach. Both methods used in tandem complement each other and can lead to a greater number of peptide identifications from a given sample. 相似文献
992.
In this paper we report the synthesis of cyclic diynes of the general formula mX2n. The letters m and n indicate the lengths of chains between two C triple bond C-X units where X indicates S, Se, or Te. The lengths of the bridges vary between m=4-8 and n=2-6. Structural investigations by means of X-ray diffraction reveal for most systems a chair-like conformation in the solid state. For 5S(2)2, 5S(2)3, 7S(2)5, 5Se(2)2 and 5Te(2)3 tubular structures were encountered. These structures can be traced back to weak XX or weak C-Hpi interactions. 相似文献
993.
CsOH-promoted epoxide ring-opening with phosphines: mild and efficient synthesis of monohydroxyphosphines 总被引:1,自引:0,他引:1
Daniel L. FoxAshlee A. Robinson James B. FrankRalph Nicholas Salvatore 《Tetrahedron letters》2003,44(41):7579-7582
A mild and convenient synthesis of monohydroxyphosphines has been achieved by epoxide ring-opening using primary or secondary phosphines in the presence of cesium hydroxide, 4 Å molecular sieves and DMF at room temperature. These reaction conditions were found to be highly regio- and stereoselective producing various monohydroxyphosphines exclusively in moderate to high yields. 相似文献
994.
The accuracy, precision, and reproducibility of a rapid method for determination of fluoride in wine, using a fluoride selective ion electrode, were established by a collaborative study involving 12 laboratories, 5 in Europe and 7 in the United States. The laboratories assayed 6 Youden pairs of fluoride-fortified, red and white wine samples with fluoride concentrations ranging from 0.2 to 3.0 mg/L. The relative standard deviations of repeatability ranged from 1.94 to 4.88%; relative standard deviations of reproducibility ranged from 4.15 to 18.40%. HORRAT values ranged from 0.30 to 0.97. The average recovery was 99.97%. Based on the statistical results of this collaborative study, the Study Director recommends that this method be adopted First Action. 相似文献
995.
Frank J. Dinan Willis T. Schwartz Roger A. Wolfe Daniel S. Hojnicki Terry St. Clair J. Richard Pratt 《Journal of polymer science. Part A, Polymer chemistry》1992,30(1):111-118
Solution and solid-state proton decoupled 13C-NMR spectra were determined on two diimides derived from 4, 4′-oxydiphthalic anhydride. Comparison of the individual diimide spectra to that of a mixture of the two diimides indicates that ordering of these materials occurs in the solid state via charge transfer complex formation. A similar study was conducted using two isomeric dianhydrides, 4, 4′-isophthaloyldiphthalic anhydride (IDPA) and 4, 4′-terephthaloyldiphthalic anhydride (TDPA). The solution spectra of these compounds are similar and are those which would be expected for these compounds. However, their solid state spectra differ from each other. The solid-state spectrum of TDPA resembles its solution spectrum, whereas, that of IDPA differs greatly from its solution spectrum and indicates charge transfer complex formation occurs with this molecule. This difference is explained in terms of the stereochemistry of the two isomeric dianhydrides. 相似文献
996.
On the basis of Altona's empirical generalization of the Karplus equation, an expression of 3JH,H as function of pseudorotation parameters for five-membered rings, was deduced. The resulting equation was parametrized by means of molecular mechanics calculations for tetrahydrofuran and tetrahydrothiophene. Estimation of 3JH,H for the full pseudorotational itinerary was made. From the best fit between calculated and measured 3JH,H values the preferred conformation of those rings may be established. The procedure was applied for the conformational analysis of 4-thiohexofuranose derivatives, having and β,
-galacto and D- manno, and -
-talo configurations. 相似文献
997.
998.
Daniel BorgisJames T. Hynes 《Chemical physics》1993,170(3):315-346
A general dynamical theory is presented for the rate constant of weak coupling, nonadiabatic proton-tunneling reactions in solution. The theory incorporates the critical role of the solvent and the vibration of the separation of the heavy particles between which the proton transfers, including their dynamics. The formulation which allows the computation of the quantum rate constant k via classical molecular dynamics simulation techniques is presented, as are a number of approximate analytic results for k in a variety of different important regimes. The frequent appearance of (nearly) classical Arrhenius behavior for k — even though the intrinsic reactive event is quantum proton tunneling — is discussed, together with the solvent and vibrational contributions to the apparent activation energy. In certain weak solvation limits, however, non-Arrhenius behavior for k is found and is related to vibrational Franck-Condon features in the reaction. 相似文献
999.
Vinyl -xylylene cross-dimerizes with other xylylene-type intermediates to yield cycloadducts of the [8+6] and [6+6] type. This reaction provides a simple entry to the [4.2]paracyclophane system as well as the analogous [4.2]cyclophanes containing furan and pyrrole moieties. 相似文献
1000.