A general procedure is proposed for the rapid development of a reversed-phase liquid chromatographic (RP-LC) separation that is "orthogonal" to a pre-existing ("primary") method for the RP-LC separation of a given sample. The procedure involves a change of the mobile-phase organic solvent (B-solvent), the replacement of the primary column by one of very different selectivity, and (only if necessary) a change in mobile phase pH or the use of a third column. Following the selection of the "orthogonal" B-solvent, column and mobile phase pH, further optimization of peak spacing and resolution can be achieved by varying separation temperature and either isocratic %B or gradient time. The relative "orthogonality" of the primary and "orthogonal" RP-LC methods is then evaluated from plots of retention for one method versus the other. The present procedure was used to develop "orthogonal" methods for nine routine RP-LC methods from six pharmaceutical analysis laboratories. The relative success of this approach can be judged from the results reported here. 相似文献
Concise total syntheses of four members of the dolabellane family of diterpenoid natural products are reported. Key features of the developed route include the first demonstration of an enantioselective, intramolecular Type I Diels-Alder macrobicyclization, the first example of a stereoselective pi-allyl Stille coupling reaction involving a farnesyl-derived intermediate, a powerful new reagent for the formation of dithianes with acid-sensitive molecules, and a unique and highly efficient ring-contraction sequence based on a modified Wolff photochemical rearrangement. 相似文献
Ion isolation in a linear ion trap is demonstrated using dual resonance frequencies, which are applied simultaneously. One frequency is used to eject ions of a broad m/z range higher in m/z than the target ion, and the second frequency is set to eject a range of ions lower in m/z. The combination of the two thus results in ion isolation. Despite the simplicity of the method, even ions of low intensity may be isolated since signal attenuation is less than an order of magnitude in most cases. The performance of dual frequency isolation is demonstrated by isolating individual isotopes of brominated compounds.
Normal mode analyses are made for methyl palmitate molecule having all-trans or conformational disorders around the ester head group, in order to explain characteristic observed frequency shifts in the wagging progressive region between all-trans and disorder chains in triglyceride molecules. It was found that one gauche conformation at C(alpha)-C(beta) position and 90 degrees rotation of the ester head group in an alkyl chain produce frequency shifts for twisting mode as observed. For wagging modes, contamination of the disorders around the head group makes assignments change and apparent frequency shifts occur. 相似文献
A series of twelve anionic, cationic, and neutral nickel(II) complexes have been synthesized and characterized. The interaction of these complexes with bovine serum albumin (BSA), human serum albumin (HSA), lysozyme (Lyso), and tryptophan (Trp) has been studied using steady-state fluorescence spectroscopy. Dynamic and static quenching constants have been calculated, and the role played in quenching by the ligand and complex charge investigated. The nickel complexes showed selectivity towards the different proteins based on the environment surrounding the Trp residue(s). Only small neutral complexes with hydrophobic ligands effectively quenched protein fluorescence via static quenching, with association constants ranging from 10(2) M(-1) (free Trp) to 10(10) M(-1) (lysozyme), indicating a spontaneous and thermodynamically favorable interaction. The number of binding sites, on average, was determined to be one in BSA, HSA and free Trp, and two in lysozyme. 相似文献
Evidence for the ground state of the neutron-unbound nucleus (26)O was observed for the first time in the single proton-knockout reaction from a 82 MeV/u (27)F beam. Neutrons were measured in coincidence with (24)O fragments. (26)O was determined to be unbound by 150(-150)(+50) keV from the observation of low-energy neutrons. This result agrees with recent shell-model calculations based on microscopic two- and three-nucleon forces. 相似文献