Optimization of mobile phase for the determination of Esomeprazole and related compounds and investigation of stress degradation by LC–MS

In this study, the objective was to investigate the degradation behavior of Esomeprazole under different recommended stress conditions according to International Conference on Harmonization of Technical Requirements for Registration of Pharmaceuticals for Human Use [1] by HPLC. Our research showed that the effect of mobile phase species on separation was significant for the determination of Esomeprazole and its related compounds. Successful separation of the drug from its related impurities and degradation products formed under different stress conditions was achieved using ammonium acetate buffer/ACN by a gradient elution. Compared with phosphate buffer/ACN, ammonium acetate buffer/ACN under same pH and gradient showed a great improvement in resolution due to the change of elution order. The drug was subjected to stress conditions including acidic, alkaline, oxidative, photolytic, and thermal conditions. Extensive degradation occurred in acidic and oxidative conditions, while mild degradation was observed in alkaline and photolytic conditions. Besides, it turned out the drug was extremely stable under thermal condition. The stability‐indicating LC–UV method was validated with respect to linearity, precision, accuracy, specificity, and robustness. The LC–MS method was also adopted for the characterization of degradation products. Based on the m/z values and fragmentation patterns, the degradation pathway of the drug has been proposed.     

Effects of nonstoichiometry on the properties of electron-doped manganite Pr0.1Ca0.9MnO3

Mn⁴⁺-rich perovskite manganites (nominal composition: Pr_0.1Ca_0.9MnO₃) were synthesized by using a citric acid method and sintered at different temperatures (800, 900, 1000, and 1300 °C) to adjust the concentration of charge carrier. All the samples are found to be in the cluster glass state at low temperature, as indicated by dc and ac magnetization. With the increase of sintering temperature, the ferromagnetic component in samples increases at first, and attains a maximum at 1000 °C, then decreases again at 1300 °C, which could be well interpreted by the change of charge carrier concentration induced by nonstoichiometry, consistent with the trend on the phase diagram. However, nonstoichiometry breaks long-range Mn-O-Mn interaction, resulting in the variance from the phase diagram.     

Chiral aminocyclopentene-based cycloaddition strategies to bicyclic [3.3.0] rings

Two cycloaddition methods were applied to chiral protected aminocyclopentenes 2 and 9 and provided novel bicyclic products 3 and 4 in good yields. The explanation for the observed stereochemistry was based on the sterically encumbered β-face forcing the cycloadditions to occur on the α-face of the cyclopentene ring. The stereochemistry of 4 was confirmed by X-ray of the fumarate salt 10 and showed the trans-relationship between the newly formed ring and the chiral –NHBoc group.     

1,1′‐[(Ethane‐1,2‐diyldioxy)di‐o‐phenylene]bis(indoline‐2,3‐dione) (L) and a novel [Ag2L2]2+ metallocycle based on coordination‐driven Ag—O and Ag—π bonds

1,1′‐[(Ethane‐1,2‐diyldioxy)di‐o‐phenylene]bis(indoline‐2,3‐dione), C₃₂H₂₄N₂O₆, L or (I), adopts a trans conformation with the two terminal indoline‐2,3‐dione groups located on opposite sides of the central ether bridge, as required by a centre of inversion located at the mid‐point of the ethane C—C bond. However, in the discrete binuclear Ag^I metallocycle complex salt bis{μ‐1,1′‐[(ethane‐1,2‐diyldioxy)di‐o‐phenylene]bis(indoline‐2,3‐dione)}disilver(I) bis(hexafluoridoantimonate), [Ag₂(C₃₂H₂₄N₂O₆)₂][SbF₆]₂, (II), synthesized by combination of L with AgSbF₆, L adopts a gauche conformation to bind Ag^Ivia the two indolinedione O atoms and two C atoms from the phenoxy ring. One dione O atom from the opposite side of the ether bridge completes the irregular coordination environment of each Ag^I atom. The complex is on a centre of inversion located between the Ag^I atoms. In the solid state, these binuclear [Ag₂L₂]²⁺ metallocycles stack together via intermolecular π–π interactions to generate a one‐dimensional chain motif, with the [SbF₆]⁻ counter‐ions, which are disordered, located between the chains.     

Numerical simulation of 2D lid‐driven cavity flow with CLEARER algorithm on extremely highly skewed grids at high Reynolds numbers

It is crucial to deal with the grid non‐orthogonality effectively in solving the flow in complex geometries, especially at high Reynolds numbers. In this study, the newly proposed Coupled and Linked Equations Algorithm Revised‐ER (CLEARER) algorithm is adopted to solve this problem successfully. In CLEARER algorithm the second relaxation factor is introduced in constructing the contravariant interface velocities, by setting it to a low value. CLEARER algorithm can overcome the severe grid non‐orthogonality and non‐linearity of equations effectively. After the numerical results with CLEARER are validated with the benchmark solutions, this algorithm is used to solve the lid‐driven flow in inclined cavity with inclination angles varying from 10 to 170^°, and Reynolds numbers varying from 5000 to 15 000. The streamlines and the centerline velocity distributions are provided in detail for all cases, which may offer some guidance for the study in this area. Copyright © 2010 John Wiley & Sons, Ltd.     

Simultaneous determination of phthalates and adipates in human serum using gas chromatography–mass spectrometry with solid‐phase extraction

A gas chromatography–mass spectrometry assay was developed and validated for the simultaneous determination of phthalates and adipates in human serum. The phthalates and adipates studied were dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzylbutyl phthalate, di‐2‐ethylhexyl phthalate, di‐n‐octyl phthalate, diethyl adipate, dibutyl adipate, diisobutyl adipate, bis(2‐butoxyethyl) adipate and di‐2‐ethylhexyl adipate, with diisooctyl phthalate as internal standard. The extraction and cleaning up procedure was carried out with solid‐phase extraction cartridges containing dimethyl butylamine groups, which showed extraction efficiencies over 88% for each analyte and the internal standard. The calibration curves obtained were linear with correlation coefficients greater than 0.98. For all analytes, the assay gave CV% values for intra‐day precision from 4.9 to 13.3% and mean accuracy values from 91.4 to 108.4%, while inter‐day precision was 5.2–13.4% and mean accuracy 91.0–110.2%. The limits of detection for the assay of phthalates and adipates were in the range 0.7–4.5 ng/mL. The method is simple, sensitive and accurate, and allows for simultaneous determination of nanogram levels of phthalates and adipates in human serum. It was successfully applied to an investigation on the level of phthalates and adipates in a non‐occupationally exposed population.     

Describing spatiotemporal couplings in ultrashort pulses using coupling coefficients

Three coupling coefficients are defined to describe spatiotemporal coupling in ultrashort pulses. With these coupling coefficients, the first-order spatiotemporal couplings of Gaussian pulse and beam are described analytically. Also, the first-order and the second-order spatiotemporal couplings caused by angular dispersion elements are studied using these coupling coefficients. It can be shown that these coupling coefficients are dimensionless and normalized, and readily indicate the severity of spatiotemporal coupling.     

整体式固相微萃取搅拌棒-分光光度法测定孔雀石绿

以开发新型吸附萃取搅拌棒为目的,利用环氧树脂、二乙基三胺和聚乙二醇（PEG 1540）通过原位逐步聚合反应制备了内封磁芯的搅拌棒.以孔雀石绿（MG）为目标分析物,详细优化了该搅拌棒吸附萃取的实验条件.在搅拌棒转速为450r？min-1和pH值为7的条件下吸附30min,然后用体积比为7：3的乙腈：乙酸铵缓冲溶液（pH 4~5）作为解吸液解吸20min.以紫外-可见分光光度计为检测手段,测定解吸液中MG的含量.该方法在0.01~5μg？mL-1的浓度范围呈现较好的线性关系,精密度和回收率较为满意.     

驱油体系化学剂间相互作用对界面吸附膜的影响

采用界面张力弛豫技术研究了不对称Gemini表面活性剂C12COONa-p-C9SO3Na、部分水解聚丙烯酰胺Mo-4000、疏水缔合水溶性聚丙烯酰胺(HMPAM)等驱油体系化学剂在癸烷/水界面上的扩张流变性质,考察了不同离子强度、不同类型电解质对体系界面流变性质的影响,计算得到界面扩张弹性模量和粘性模量的全频率谱,并通过归一化方法(cole-cole图)探讨了界面吸附膜的弛豫过程。研究发现,界面膜内分子重排和界面与体相间分子扩散交换是影响膜性质的主要弛豫过程。表面活性剂体相浓度增大有利于界面分子重排过程,而低频有利于扩散交换过程;不同结构聚合物以及不同离子强度、不同类型电解质对表面活性剂吸附膜有不同的影响。