Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

Kinetic Buffers

This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH‐sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH–t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di‐copper(II) bistren complex in a single run, in a completely automatic experiment.     

Use of quasi-isoelectric buffers to limit protein adsorption in capillary zone electrophoresis

The use of quasi-isoelectric buffers consisting of narrow pH cuts of carrier ampholytes (NC) has been investigated to limit protein adsorption on capillary walls during capillary zone electrophoresis experiments. To quantify protein adsorption on the silica surface, a method derived from that of Towns and Regnier has been developed. alpha-Lactalbumin (14 kDa, pI 4.8) and alpha-chymotrypsinogen A (25 kDa, pI 9.2) have been used as model proteins. Acidic narrow pH cuts of carrier ampholytes (NC, pH 3.0) obtained from fractionation of Serva 4-9 carrier ampholytes were used as BGE in bare-silica capillaries, and allowed to decrease significantly protein adsorption, as compared to experiments performed with classical formate buffer. The use of NC as BGE appeared to be as efficient as the use of polydimethylacrylamide coating to prevent protein adsorption. This increase of protein recovery when using NC was attributed to the interaction of carrier ampholytes with the silica surface, leading to a shielding of the capillary wall.     

两款原子吸收光谱仪的塞曼背景校正装置

讨论了永久磁场塞曼背景校正原子吸收光谱仪的外光路和磁场的设计工艺,描述了可以同时获得交流磁场和直流磁场塞曼背景校正测定结果的新系统,以及可以克服洛伦兹力对测定产生影响的磁场和石墨炉的供电系统.     

Off-diagonal long-range order of the wave function in terms of the alternate molecular bonding geminals

It is shown that in the quantum structural approach to high-Tc superconductivity, the wave function in terms of the alternate molecular bonding geminals possesses off-diagonal long-range order (ODLRO).     

螺旋天线步进电机控制系统仿真及运行曲线优化

为实现机械相控阵列天线的波束扫描,采用步进电机驱动螺旋天线单元转动来达到预定的辐射相位。为了优化步进电机的开环控制,研究运行曲线对步进电机控制性能的影响,提高步进电机控制速度和精度。根据步进电机及控制系统的工作原理,建立了基于Simulink的步进电机开环控制系统仿真模型,并在此基础上对梯形和抛物线两种运行曲线进行了仿真研究。仿真结果表明,该仿真模型能精确实现两种运行曲线对步进电机的控制,在100 ms的控制周期内,采用梯形运行曲线步进电机的最大无失步转动角度能够达到270,而采用抛物线运行曲线时其转动角度能够达到360,抛物线运行曲线在开环控制系统中具有更高的控制速度。     

Solvation consequences of polymer PVP with biological buffers MES,MOPS, and MOPSO in aqueous solutions

Densities and viscosities were measured for the aqueous buffer (MES, MOPS, or MOPSO) solutions containing different concentrations of polyvinylpyrrolidone (PVP) (5, 10, 15, 20 and 30) mass% at temperatures from (298.15 to 318.15) K under atmospheric pressure. The DFT calculations were also performed and the binding energies of the possible (PVP + buffer) complexes were obtained. The experimental and computational results reveal the interactions of the PVP with the constituent compounds in the aqueous buffer solutions. Additionally we have explored the solvation behavior of the buffers by measuring the densities and the viscosities data of the aqueous buffer solutions from (0.0 to 1.0) mol · kg⁻¹ at temperatures from (298.15 to 318.15) K. The viscosity results were correlated with the Jones–Dole equation. The correlated results confirmed that all the investigated buffers behave as Kosmotropes (structure makers).     

Alternate pacing of border-collision period-doubling bifurcations

Unlike classical bifurcations, border-collision bifurcations occur when, for example, a fixed point of a continuous, piecewise C ¹ map crosses a boundary in state space. Although classical bifurcations have been much studied, border-collision bifurcations are not well understood. This paper considers a particular class of border-collision bifurcations, i.e., border-collision period-doubling bifurcations. We apply a subharmonic perturbation to the bifurcation parameter, which is also known as alternate pacing, and we investigate the response under such pacing near the original bifurcation point. The resulting behavior is characterized quantitatively by a gain, which is the ratio of the response amplitude to the applied perturbation amplitude. The gain in a border-collision period-doubling bifurcation has a qualitatively different dependence on parameters from that of a classical period-doubling bifurcation. Perhaps surprisingly, the differences are more readily apparent if the gain is plotted versus the perturbation amplitude (with the bifurcation parameter fixed) than if plotted versus the bifurcation parameter (with the perturbation amplitude fixed). When this observation is exploited, the gain under alternate pacing provides a useful experimental tool to identify a border-collision period-doubling bifurcation.     

化学跑合剂对跑合效果的影响

在ＢＪ５２Ａ胶合试验机、ＪＰ－ＢＤ１５００型接触疲劳试验机和ＣＬ－１００齿轮试验机上考察了化学跑合剂的作用，并就其机理进行了探讨。结果表明：采用化学跑合剂跑合后，表面粗糙度明显降低；表面接触面积增大，可以实现１次满载快速跑合；与采用含磨料的跑合方法比较，化学跑合剂可以明显提高表面接触精度，减少裂纹源的发生和发展，使表面承载能力明显提高。当齿轮加工精度较低或高速、重载齿轮的硬齿面精加工存在困难时，可     

基于ASME应变限制准则的小冲杆试验等效断裂应变

为更清楚地了解阳江35kV服役导线的运行状态,从分析导线断线原因出发,通过对老旧导线的单丝断裂强度、弹性模量、应力应变曲线、拉断力、抗拉强度等综合指标的测试与分析,研究服役导线的力学性能,由试验结果得出：35kV老旧导线钢芯的直径变化对于架空导线的外径变化有直接的影响,老旧导线的铝线直径变化较小,其外径增大1.67％~4.24％;钢单线的拉断应力仍能达到标准中规定值的106%,且伸长率也满足要求;部分铝线的抗拉强度低于95%;绞线拉断力仍能达到95%的计算拉断力。但是相同规格下的老旧导线的抗拉强度比新导线的抗拉强度低2%~18%。结果表明：阳江地区服役三十年以上的老旧导线在力学性能上仍能继续承载。