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101.
Two ligand exchange chiral stationary phases (CSPs) based on (S)-leucinol derivative, sodium N-((S)-1-hydroxymethyl-3-methylbutyl)-N-undecylaminoacetate, and (R)-phenylglycinol derivative, sodium N-((R)-2-hydroxy-1-phenylethyl)-N-undecylaminoacetate, covalently bonded to silica gel have been successfully applied in the resolution of nine -hydroxycarboxylic acids. The latter was more effective than the former, the separation factors () being 1.05 to 2.12 while the resolution factors (RS) varying from 0.18 to 5.29 on the latter. The chromatographic resolution behaviors were dependent on the type and the content of organic modifier and the content of CuSO4 in aqueous mobile phase and the column temperature. A possible chiral recognition mechanism was also proposed based on the chromatographic resolution behaviors. 相似文献
102.
103.
Synthesis, Crystal Structure and Spectroscopic Properties of the Cluster Anions [(Mo6Br )X ]2? with Xa = F, Cl, Br, I The tetrabutylammonium (TBA), tetraphenylphosphonium (TPP) and tetraphenylarsonium (TPAs) salts of the octa-μ3-bromo-hexahalogeno-octahedro-hexamolybdate(2?) anions [(Mo6Br)X]2? (Xa = F, Cl, Br, I) are synthesized from solutions of the free acids H2[(Mo6Br)X] · 8 H2O with Xa = Cl, Br, I. The crystal structures show systematic stretchings in the Mo? Mo bond length and a slight compression of the Bri8 cube in the Fa to Ia series. The cations do not change much. The i.r. and Raman spectra show at 10 K almost constant frequencies of the (Mo6Bri8) cluster vibrations, whereas all modes with Xa ligand contribution are characteristically shifted. The most important bands are assigned by polarization measurements and the force constants are derived from normal coordinate analysis. The 95Mo nmr signals are shifted to lower field with increasing electronegativity of the Xa ligands. The fluorine compound shows a sharp 19F nmr singlet at ?184.5 ppm. 相似文献
104.
V. Ya. Kavun N. A. Didenko A. B. Slobodyuk I. A. Tkachenko A. V. Gerasimenko N. F. Uvarov V. I. Sergienko 《Journal of Structural Chemistry》2005,46(5):839-847
The mobility of fluoride and ammonium ions (180–480 K) in compounds K2? n (NH4)nZrF6 (0.2 ≤ n ≤ 1.70) was investigated by 19F and 1H NMR. Correlations have been found between the composition of the cation sublattice, the character of ion motions, and phase transition temperature in these compounds. The hightemperature modifications with n ≥ 0.85 of the compounds are characterized by translational diffusion of fluoride and ammonium ions and by uniaxial anisotropy of the 19F magnetic shielding tensor. The electrophysical characteristics of these compounds were studied in the temperature range 300–480 K. 相似文献
105.
Densification of boron carbide during sintering may be improved by a two-stage process, namely heating to 2000°C under vacuum and sintering at 2190°C under argon. This sintering regime allows achieving a relative density of the ceramic bodies fabricated from a fine powder higher than 95%. The nitrogen treatment of the boron carbide phase at 1900°C leads to the formation of the BN phase and precipitation of graphite. Vacuum treatment of these samples at 2000°C leads to decomposition of the boron nitride phase. The liberated free boron may again react with graphite to form in situ boron carbide particles. The experimental investigations of the sintering behavior of the boron carbide phase under various atmospheres supported the thermodynamic predictions regarding the phase transformation. No evidence, however, was found for enhanced sintering under a nitrogen atmosphere. 相似文献
106.
107.
C. I. J. M. Stuart 《Foundations of Physics Letters》1991,4(5):479-492
Aprediction puzzle leads to a form ofnecessary realism which forces the rejection of a central tenet of the Copenhagen interpretation. This leads to reconsidering conceptual difficulties related to Bell's locality premise. It is shown that aparadox of elementary probability theory puts new light on Bell's assumption that causality and statistical independence are mutually incompatible.
Nemo dat quod non habet : No one can offer more than he has ability to give; in that spirit, this paper is dedicated to the memory of J.S. Bell. 相似文献
108.
We investigate the application of torsion angle molecular dynamics (TAMD) to augment conformational sampling of peptides and proteins. Interesting conformational changes in proteins mainly involve torsional degrees of freedom. Carrying out molecular dynamics in torsion space does not only explicitly sample the most relevant degrees of freedom, but also allows larger integration time steps with elimination of the bond and angle degrees of freedom. However, the covalent geometry needs to be fixed during internal coordinate dynamics, which can introduce severe distortions to the underlying potential surface in the extensively parameterized modern Cartesian-based protein force fields. A "projection" approach (Katritch et al. J Comput Chem 2003, 24, 254-265) is extended to construct an accurate internal coordinate force field (ICFF) from a source Cartesian force field. Torsion crossterm corrections constructed from local molecular fragments, together with softened van der Waals and electrostatic interactions, are used to recover the potential surface and incorporate implicit bond and angle flexibility. MD simulations of dipeptide models demonstrate that full flexibility in both the backbone phi/psi and side chain chi1 angles are virtually restored. The efficacy of TAMD in enhancing conformational sampling is then further examined by folding simulations of small peptides and refinement experiments of protein NMR structures. The results show that an increase of several fold in conformational sampling efficiency can be reliably achieved. The current study also reveals some complicated intrinsic properties of internal coordinate dynamics, beyond energy conservation, that can limit the maximum size of the integration time step and thus the achievable gain in sampling efficiency. 相似文献
109.
Shan Qian Li Hai Lei Tang Jin Cheng Yang Yong Wu 《中国化学快报》2007,18(3):261-262
An optically active intermediate 5 for A-ring of 19-nor-1a,25-dihydroxyvitamin D3 2 has been synthesized in five steps, starting from readily available, inexpensive D( )-xylose 6 with good yield. 相似文献
110.
Jun Li 《Journal of Cluster Science》2002,13(1):137-163
The electronic structures and bonding of isopoly oxometalates M6O19
2– (M=Cr, Mo, W) have been investigated by using ab initio and relativistic density functional methods. We have discussed the role of the central oxygen atom and the (d-p) conjugation interactions between the metal and bridging oxygen atoms. It is found that there exist 12 three-centered two-electron (d-p-d) bonds for the three M4(-O)4 planar rings in M6O19
2– ions and these hexametalates are considered to have quasi-aromaticity. The (d-p) conjugation effects play essential role in stabilizing these cluster compounds, and the reduced (d-p) conjugation effects account for the instability of the isopoly oxochromate ion, Cr6O19
2–. The vibrational spectra and electronic spectra of M6O19
2– ions are evaluated and assigned theoretically and the calculated spectra are in fairly good agreement with the measured experimental results. 相似文献