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61.
A synthesis of N-acetylcolchinol, a key intermediate in the synthesis of ZD6126, was developed. The enantiodifferentiating step required the catalytic asymmetric hydrogenation of an enamide. After screening a range of metal and ligand combinations it was found that (S,S)-iPr-FerroTANE Ru(methallyl)2 and [(S,S)-tBuFerroTANE Rh(COD)]BF4 gave both high enantioselectivity (>90% ee) and high catalyst utility (molar S/C = 1000). 相似文献
62.
A series of commercial monomeric and polymeric C(18), C(27), and C(30) stationary phases were compared with immobilized poly(ethylene-co-acrylic acid) stationary phases synthesized in-house. The columns were characterized on the basis of methylene selectivity, silanol activity, metal activity, pore size, shape selectivity, and the ability to separate tocopherol isomers and carotenoid isomers. Monomeric and polymeric C(30) phases were shown to yield excellent separations of the tocopherol isomers while the polymeric C(30) and polyethylene phases were more appropriate to the separation of carotenoids. 相似文献
63.
Odile Meyer Jean-Franois Hoeffler Catherine Grosdemange-Billiard Michel Rohmer 《Tetrahedron》2004,60(52):12153-12162
An optimised gram scale synthesis allows the production of 1-deoxy-d-xylulose and 1-deoxy-d-xylulose 5-phosphate with possible deuterium labelling at C-5. Such substrates are required for investigations on the mevalonate-independent 2-C-methyl-d-erythritol 4-phosphate pathway for isoprenoid biosynthesis in bacteria and chloroplasts of phototrophic eukaryotes and for the biosynthesis of vitamins B1 (thiamine diphosphate) and B6 (pyridoxol phosphate) in bacteria. 相似文献
64.
The effect of nine peak measurement/analysis parameters on chiral capillary electrophoresis (CE), followed by UV detection, was studied. The parameters pertained UV-detection (detection wavelength, reference wavelength, and wavelength bandwidths), signal processing (data acquisition rate, type and amount of filtering) and peak detection (detection threshold and peak width). The influence of these factors on the chiral separation of dimethindene enantiomers was studied at two different concentrations (i.e., at high and low signal-to-noise (S/N) ratio) by the means of experimental designs. The electropherogram characteristics considered were the resolution between the two enantiomers, the peak areas, and the S/N ratio. A D-optimal design was first used as screening design to identify the most critical parameters. Afterwards, a modelling of the different responses as a function of these critical parameters was performed based on the results of a face-centered central composite design. The results showed that the signal-processing parameters should be carefully selected when developing a CE separation since very important variations in the separation, the S/N ratio and the peak area of the substances can occur by setting these parameters at different levels. The detection wavelength should also be carefully chosen for optimal peak area measurement. The role of these parameters becomes more important with decreasing concentration of the analytes (i.e., low S/N ratio). This study showed that the peak measurement/analysis parameters should be optimized as the chemical and physical parameters of a method. They also should always be well specified in order to allow a good transfer of a method from one instrument to another. 相似文献
65.
Sajal Sen Mark W. Perrin Adam C. Sedgwick Vincent M. Lynch Jonathan L. Sessler Jonathan F. Arambula 《Chemical science》2021,12(21):7547
Recent decades have witnessed the emergence of Au(i) bis-N-heterocyclic carbenes (NHCs) as potential anticancer agents. However, these systems exhibit little interaction with serum proteins (e.g., human serum albumin), which presumably impacts their pharmacokinetic profile and tumor exposure. Anticancer drugs bound to human serum albumin (HSA) often benefit from significant advantages, including longer circulatory half-lives, tumor targeted delivery, and easier administration relative to the drug alone. In this work, we present Au(i) bis-NHCs complexes, 7 and 9, capable of binding to HSA. Complex 7 contains a reactive maleimide moiety for covalent protein conjugation, whereas its congener 9 contains a naphthalimide fluorophore for non-covalent binding. A similar drug motif was used in both cases. Complexes 7 and 9 were prepared from a carboxylic acid functionalized Au(i) bis-NHC (complex 2) using a newly developed post-synthetic amide functionalization protocol that allows coupling to both aliphatic and aromatic amines. Analytical, and in vitro techniques were used to confirm protein binding, as well as cellular uptake and antiproliferative activity in A549 human lung cancer cells. The present findings highlight a hitherto unexplored approach to modifying Au(i) bis-NHC drug candidates for protein ligation and serve to showcase the relative benefits of covalent and non-covalent HSA binding.Au(i) bis-N-heterocyclic carbenes (NHCs) functionalized using an amide linker were found to bind to human serum albumin (HSA) in covalent and non-covalent fashion. The solubility and in vitro anti-cancer activity of these new conjugates were studied. 相似文献
66.
Castro C Karney WL Valencia MA Vu CM Pemberton RP 《Journal of the American Chemical Society》2005,127(27):9704-9705
Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes. 相似文献
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70.
Catherine J. Murphy 《Journal of Cluster Science》1996,7(3):341-350
One of the most exciting frontiers in materials chemistry in recent years is the optoelectronics of quantum-confined semiconductor nanoclusters. These nanoclusters are 10–200 A in diameter, and in this size regime exhibit extra-ordinarily interesting quantum mechanical effects. Cadmium sulfide is a popular semiconductor for these studies, and reviewed here is the synthesis and charac-terization of such CdS nanoclusters, with emphasis on how chemical control of the surface by thiolates influences product formation and properties. Also described are the syntheses and structures of true molecular clusters of CdS capped with thiolate ligands. 相似文献