排序方式: 共有65条查询结果,搜索用时 328 毫秒
41.
A new class of regioselectively substituted amylose derivatives bearing three different substituents at 2-, 3- and 6-positions, and two different substituents at 2-position and 3-, 6-positions were synthesized by a sequential process based on the esterification of 2-position of a glucose unit. Their chiral recognition abilities were evaluated as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). Each derivative had its own characteristic recognition ability depending on the arrangement of side chains at the three positions. Among the derivatives, amylose 2-(4-t-butylbenzoate) and amylose 2-(4-chlorobenzoate) series exhibited high chiral recognition. Some racemates can be efficiently separated on these derivatives as well as on the amylose tris-3,5-dimethylphenylcarbamate, which is commercially available as Chiralpak AD and one of the most powerful CSPs. The structures of the amylose derivatives were also investigated by circular dichroism spectroscopy. 相似文献
42.
Fast semipreparative HPLC enantioseparation of four axially chiral biscarbostyrils (4,4′-bisquinoline-2-ones) using ULMO as a π-acidic Pirkle type chiral stationary phase leads to two racemizing pairs (1,2; kobs 1.6 × 10−4 and 3.0 × 10−4 s−1 at 28 °C) and two stable ones (3,4). 3 was stabilized by a crown ether linkage from pos. 6 to 6′, and 4 had sterically demanding bromo substituents in pos. 3 and 3′. On-column generated temperature-dependent chromatograms of 1 and 2 were fitted with Auto-DHPLCy2k and DCXplorer. For cpd 2 both programs delivered similar ΔG values of 90 and 93 kJ/mol, well comparable with the 99 kJ/mol calculated with the B3LYP/6-31G (d) procedure. At temperatures of high conversion DCXplorer delivered inconsistent series of rate constants for the more tailing and less resolved tetramethoxy derivative 1. We connect this problem with an almost impossible halfwidth calculation of tailing peak pairs which are weakly resolved. However, this problem could be observed only in the case of tetramethoxy derivative 1. Stochastic generated data of Auto-DHPLCy2k could be used at a lower percentage of conversion only while the theoretical plate model did not deliver useful data at temperatures of very low conversion but fitted well high conversion chromatogram series of 1 and 2. 相似文献
43.
This article is concerned with
the asymptotic accuracy of the
Computational Singular Perturbation (CSP)
method developed by Lam and Goussis [The CSP method for simplifying kinetics,
Int. J. Chem. Kin. 26 (1994) 461–486]
to reduce the dimensionality of a
system of chemical kinetics equations.
The method,
which is generally applicable to
multiple-time scale problems
arising in a broad array of scientific disciplines,
exploits the presence of
disparate time scales to model
the dynamics by an evolution equation
on a lower-dimensional slow manifold.
In this article it is shown that
the successive applications
of the CSP algorithm generate,
order by order,
the asymptotic expansion
of a slow manifold.
The results are illustrated
on the Michaelis–Menten–Henri
equations of enzyme kinetics. 相似文献
44.
Fungicides are very important and diverse environmental and agricultural concern species. Their determination in commercial formulations or environmental matrices, requires highly efficient, selective and sensitive methods. A significant number of these chemicals are chiral with the activity residing usually in one of the enantiomers. The different toxicological and degradation behavior observed in many cases for fungicide enantiomers, results in the need to investigate them separately. For this purpose, separation techniques such as GC, HPLC, supercritical fluid chromatography (SFC) and CE have widely been employed although, at present, HPLC still dominates chromatographic chiral analysis of fungicides. This review covers the literature concerning the enantiomeric separation of fungicides usually employed in agriculture grouping the chiral separation methodologies developed for their analysis in environmental, biological, and food samples. 相似文献
45.
《Journal of Coordination Chemistry》2012,65(4):457-464
In our series of investigations into the structural and thermal behaviour of metal thiourea (tu) complexes, the single-crystal X-ray structure of dichlorobis(thiourea-S)-zinc(II) is redetermined at higher accuracy to R?=?0.0315 proving the space group Pnma. Half of the complex molecule is in the asymmetric unit, the Zn and the two Cl atoms lie on the mirror plane. The structure analysis shows tetrahedral coordination of the Zn cation, the coordination sphere of the chloride anions and the extended hydrogen bond network. A chloride ligand is situated in the middle of the sandwich formed by bilayers of the complex molecules. We previously characterized the Cd analogue, allowing a structural comparison between the non-isostructural complexes: Mtu2Cl2 (M?=?Zn, Cd). Also the thermal properties of the complexes and their behaviour in chemical spray pyrolysis (CSP) processes are briefly correlated with the structure and bonding. 相似文献
46.
本文报道了我们所研制的沟槽衬底平面条形(CSP)铝镓砷((AlGa)As)单模激光器,能以单纵模稳定工作,△v<5MHz,并从理论上定性分析了半导体激光器线宽变宽的机理,提出了进一步压窄线宽的方法. 相似文献
47.
48.
采用纤维素-三(4-甲基苯甲酸酯)手性固定相,利用反相高效液相色谱法研究了奥沙西泮、吡格列酮和罗格列酮3种含氮杂环类手性药物的色谱拆分行为.考察了流动相组成、pH值和柱温对3种药物对映体分离的影响,并对其拆分机理进行了探讨.结果表明,采用甲醇-水为流动相,通过添加醋酸或氨水调节pH值和控制柱温,可使3种药物的对映体得到完全分离(Rs>1.5),根据各自优化的色谱条件建立了这3种手性药物对映体的分析方法,并应用于其制剂的含量测定,方法简单、可靠. 相似文献
49.
将纤维素-三(3,5-二甲基苯基氨基甲酸酯)(CDMPC)涂敷于氨丙基硅胶上制备成高效液相色谱(HPLC)手性固定相,对手性农药顺式、反式氯氰菊酯和烯唑醇对映异构体在正相条件下进行了手性拆分。分别以正己烷和石油醚为流动相,考察改性剂的含量;在正己烷流动相条件下考察了色谱柱长度、温度对拆分效果的影响。试验结果显示,改性剂含量的减少、长色谱柱及降低温度均有利于对映体的分离。该手性固定相对顺式、反式氯氰菊酯具有非常强的立体选择性,对烯唑醇也有较好的拆分能力。 相似文献
50.
面向短时宽带声源实时定向问题,提出了一种基于互功率谱时延估计的十字阵定向优化算法。针对该方法估计结果离散且呈不均匀分布的特点,将观测平面划分为四个测量区域,并利用不同阵元组合分别处理,解决实时性与估计成功率的矛盾;依据互相关函数的特点,设计了若干判断准则,排除由于数据取样短造成的异常时延估计,改善算法的可靠性;采用频域插值方法,一定程度上提高时延估计精度,从而提高定向精度。MATLAB仿真和DSP系统实验表明,这种方法在实际应用中有效提高了对短时宽带声源定向的性能。 相似文献