Combined use of ionic liquid and β‐CD for enantioseparation of 12 pharmaceuticals using CE

In this study, the enantioseparation of zopiclone, repaglinide, chlorphenamine maleate, brompheniramine maleate, dioxopromethazine hydrochloride, promethazine hydrochloride, liarozole, carvedilol, homatropine hydrobromide, homatropine methylbromide, venlafaxine, and sibutramine hydrochloride has been investigated using β‐CD in combination with a chiral ionic liquid (IL), 1‐ethyl‐3‐methylimidazolium‐L‐lactate. The influence of the type of IL and its concentration, BGE pH, and chain length of the IL cations on the resolution are discussed. Finally, the proposed method was successfully applied for the chiral impurity determination of eszopiclone in pharmaceutical tablets after validation with respect to accuracy and precision, linearity range, selectivity, repeatability, LOD and LOQ. It is assessed that the chiral impurity determination in the commercial tables is fewer than 0.1%.     

Fisher Information of Free-Electron Landau States

An electron in a constant magnetic field has energy levels, known as the Landau levels. One can obtain the corresponding radial wavefunction of free-electron Landau states in cylindrical polar coordinates. However, this system has not been explored so far in terms of an information-theoretical viewpoint. Here, we focus on Fisher information associated with these Landau states specified by the two quantum numbers. Fisher information provides a useful measure of the electronic structure in quantum systems, such as hydrogen-like atoms and under some potentials. By numerically evaluating the generalized Laguerre polynomials in the radial densities, we report that Fisher information increases linearly with the principal quantum number that specifies energy levels, but decreases monotonically with the azimuthal quantum number m. We also present relative Fisher information of the Landau states against the reference density with m=0, which is proportional to the principal quantum number. We compare it with the case when the lowest Landau level state is set as the reference.     

四川省市州经济发展差异的统计分析

采用因子分析研究四川省21市州之间的相关性,利用主因子计算出各个市州得分,以市州得分作为新变量进行集团排序,再将基于相对位置排序法引入到集团排序中,进而得到最终的市州分类结果,在统计分析的基础上对市州经济发展给出一些建议.     

Robustness in deterministic multi-objective linear programming with respect to the relative interior and angle deviation

This paper deals with the robustness issue in deterministic multi-objective linear programming from two new standpoints. It is shown that a robustness notion recently reported in the literature is equivalent to strict efficiency. Corresponding to an efficient solution, a new quantity, robustness order (RO) is defined with respect to the interiority order of the cost matrix in the binding cone. A linear programming problem is provided to calculate the RO of a given efficient solution. The second part of the paper is devoted to investigating the robustness with respect to the eligible angle deviation of the cost matrix in the binding cone. Theoretical results are given to obtain the maximum eligible angle deviation. Finally, the relationship between two above-mentioned robustness standpoints is established. To have a better geometrical view, we prove the results for single-objective LP problems at first, and then we extend them to the multi-objective case. In addition to the theoretical results, some clarifying examples are given.     

Power of isotopic fine structure for unambiguous determination of metabolite elemental compositions: In silico evaluation and metabolomic application

In mass spectrometry (MS)-based metabolomics studies, reference-free identification of metabolites is still a challenging issue. Previously, we demonstrated that the elemental composition (EC) of metabolites could be unambiguously determined using isotopic fine structure, observed by ultrahigh resolution MS, which provided the relative isotopic abundance (RIA) of ¹³C, ¹⁵N, ¹⁸O, and ³⁴S. Herein, we evaluated the efficacy of the RIA for determining ECs based on the MS peaks of 20,258 known metabolites. The metabolites were simulated with a ≤25% error in the isotopic peak area to investigate how the error size effect affected the rate of unambiguous determination of the ECs. The simulation indicated that, in combination with reported constraint rules, the RIA led to unambiguous determination of the ECs for more than 90% of the tested metabolites. It was noteworthy that, in positive ion mode, the process could distinguish alkali metal-adduct ions ([M + Na]⁺ and [M + K]⁺). However, a significant degradation of the EC determination performance was observed when the method was applied to real metabolomic data (mouse liver extracts analyzed by infusion ESI), because of the influence of noise and bias on the RIA. To achieve ideal performance, as indicated in the simulation, we developed an additional method to compensate for bias on the measured ion intensities. The method improved the performance of the calculation, permitting determination of ECs for 72% of the observed peaks. The proposed method is considered a useful starting point for high-throughput identification of metabolites in metabolomic research.     

Quantitative NMR (qNMR) for pharmaceutical analysis: The pioneering work of George Hanna at the US FDA

In the last two decades, quantitative NMR (qNMR) has become increasingly important for the analysis of pharmaceuticals, chemicals, and natural products including dietary supplements. For the purpose of quality control and chemical standardization of a large variety of pharmaceutical, chemical, and medicinal products, qNMR has proven to be a valuable orthogonal quantification method and a compelling alternative to chromatographic techniques. This work reviews a fundamental component of the early development of qNMR, reflected in the pioneering work of the late George M. Hanna during the years between 1984 and 2006 at the US Food and Drug Administration (FDA). Because Hanna performed the majority of his groundbreaking work on a 90‐MHz instrument, his legacy output connects with recent progress in low‐field benchtop NMR instrumentation. Hanna gradually established the utility of qNMR for the routine quality control analyses practiced in pharmaceutical and related operations well ahead of his peers. His work has the potential to inspire new developments in qNMR applied to small molecules of biomedical importance.     

基于假设脱钩区间模型的省际节能减排压力测算以辽宁省为例

参照资源消耗及废物排放与经济增长的定量表达式-IGT方程和IGTX方程,分别推导出资源脱钩指数和二氧化碳排放指数方程.根据脱钩指数,将二氧化碳排放与GDP脱钩程度分为绝对脱钩、相对脱钩和未脱钩三种程度,并构建了假设相对脱钩和假设绝对脱钩区间.以辽宁省1995-2012年间二氧化碳排放量和GDP增长量为对象,分析了二者的脱钩关系.研究发现,除了1997和1999年二者处于相对脱钩状态,其余年份均未脱钩.运用假设脱钩区间模型,分别计算达到相对脱钩和绝对脱钩状态的二氧化碳年排放理想值,并与现值进行比较,得到各年节能减排的压力值.研究结果表明:相对脱钩的压力相对较小,减排压力在0-1671万t之间,占基准年碳排放量的0%-12.23%;绝对脱钩的压力较大,减排压力在320.77-4899.84万t,占基准年碳排放量的2.35%-23.94%.     

NMR 77Se, 125Te, 31P and Structure of Seleno-and Telluro-Phosphorus Compounds

Spectra of a nuclear magnetic resonance of seleno- and telluro-phosphorus compounds on nuclei ⁷⁷Se, ¹²⁵Te, ³¹P are described. The dependences of spectral parameters on a structure of the substitutes at phosphorus atom in these compounds are discussed.     

Efficient separation of high‐purity compounds from Oxytropis falcata using two‐dimensional preparative chromatography

The separation of high‐purity compounds from traditional Tibetan medicines plays an important role in investigating their bioactivity. Nevertheless, it is often quite difficult to isolate compounds with high purity because of the complexity of traditional Tibetan medicines. In this work, an offline two‐dimensional reversed‐phase preparative method was successfully developed for the separation of high‐purity compounds from Oxytropis falcata . Based on the analysis results, an ODS C18 prep column was used for first‐dimensional preparation, and 14.8 g of the crude sample was separated into five fractions with a recovery of 74.6%. Then, an XAqua C18 prep column was used to isolate high‐purity compounds in the second‐dimensional preparation because its separation selectivity is different with the ODS C18 stationary phase. As a result, eight compounds in the crude sample were isolated in more than 98% purity. This is the first report of trans‐cinnamic acid ( 1 ) and trifolirhizin ( 2 ) from Oxytropis falcata . This method has the potential to be an efficient separation method of high‐purity compounds from Oxytropis falcata and it shows great promise for the separation of high‐purity compounds from complex samples.     

地球静止轨道远程交会过程导航性能评估

远程交会是静止轨道共位卫星自主定点置入的关键途径。针对远程交会过程中大距离跨度下相对运动模型的误差信号特性,理论推导了误差的传递机理,给出了相对导航EKF算法期望及噪声特性的定量分析模型。研究表明,确定距离区间存在最优过程噪声量级及其对应的最优滤波性能,且滤波误差与交会距离正相关,可作为全局最优滤波器的定量设计依据,解决了静止轨道远程交会过程EKF导航算法性能的量化评估问题。仿真表明,分析结论正确,相对速度滤波误差全程优于0.005 m/s(1σ),满足交会任务需求。