Sample plug induced peak splitting in capillary electrophoresis studied using dual backscattered interferometry and fluorescence detection

The appearance of unexpected peaks in capillary electrophoresis (CE) is common and can lengthen the time of method development as assay conditions and experimental parameters are varied to understand and mitigate the effects of the additional peaks. Additional peaks can arise when a single-analyte zone is split into multiple zones. Understanding the underlying mechanism of these phenomena, recognizing conditions that favor its presence, and knowing how to confirm and eliminate the effect are important for efficient method optimization. In this study, we examine how the overlap of analyte zones with the sample plug can lead to peak splitting. This is explored experimentally using dual detection CE, which enables both the sample plug and analyte zones to be independently and simultaneously measured from the same detection volume. Simulations performed via COMSOL Multiphysics confirm the origin of the splitting and help guide experiments to reduce and eliminate the effect. Our findings show that this peak splitting mechanism can arise in separations of both small and large molecules but is, especially, prevalent in separations of slowly migrating macromolecules. This effect is also more prevalent when using a short length-to-detector, as is commonly found in microfluidic applications. A simple diffusion-less model is introduced to develop strategies for reducing peak splitting that avoids modifying the apparatus, such as by lengthening the separation length, which can be difficult. Decreasing the sample plug length and slowing the electroosmotic flow can both reduce this effect, which is confirmed experimentally.     

Theoretical investigation on dual fluorescence and intramolecular charge transfer of 5-phenyl-5H-phenanthridin-6-one

Quantum-chemical calculations with the time-dependent density function theory (TDDFT) have been carried out for 5-phenyl-5H-phenanthridin-6-one (PP). For this molecule, dual fluorescence and in- tramolecular charge transfer (ICT) were experimentally observed. The B3LYP functional with 6-311 G (2d, p) basis set has been used for the theoretical calculations. The solvent effects have been described within the polarizable continuum model (PCM). Ground-state geometry optimization reveals that the phenyl/phenanthridinone dihedral angle equals 90.0°, a nearly perpendicular structure. Vertical ab- sorption energy calculations characterize the lower singlet excited states both in gas phase and in solvents. It can be found that the lower excited states have locally excitation (LE) feature. Through constructing the potential energy curves of both isolated and solvated systems describing the LE→ICT reaction and fluorescence emission, we obtain the enthalpy difference ΔH between the LE and ICT states, energy barrier Ea, and energy difference δEFC, indicating the structural changes taking place during the ICT reaction. Potential curve and calculated emission energies for both isolated and sol- vated systems show a dual fluorescence phenomenon, consisting of a LE emission band and a red-shifted ICT band. Our calculations including the solvent effects indicate that the dual fluorescence is brought about by the change in molecular structure connected with the planarization of the twisted N-phenylphenanthridinone during the ICT reaction.     

Synthesis and characterization of dual‐responsive micrometer‐sized core‐shell composite polymer particles

Dual‐responsive micrometer‐sized core‐shell composite polymer particles were prepared by dispersion polymerization followed by seeded copolymerization. Polystyrene (PS) particles prepared by dispersion polymerization were used as core particles. N‐isopropyl acrylamide (NIPAM) and methacrylic acid (MAA) were used to induce dual‐responsive that is thermo‐ and pH‐responsive properties in the shell layer of composite polymer particles, prepared by seeded copolymerization with PS core particles. Temperature‐ and pH‐dependent adsorption behaviors of some macromolecules on composite polymer particles indicate that produced composite polymer particles exhibit dual‐responsive surface properties. Copyright © 2007 John Wiley & Sons, Ltd.     

关于Smarandache对偶函数

定义Smarandache对偶函数S*(n)为最大的正整数m使得m!|n.定义另一种双阶乘函数S**(n)为最大的正整数2m-1使得(2m-1)!!|n,其中2 n;且当2|n时,为最大的正整数2m使得(2m)!!|n.本文的主要目的是利用初等方法研究一个包含S**(n)的无穷级数的收敛性,并给出一个有趣的恒等式.     

基于晶体塑性有限元的多晶铜力学行为研究

通过晶体塑性有限元对Voronoi多晶铜的单调拉伸和循环塑性行为进行数值模拟. 单调拉伸的模拟结果发现多晶体的力学响应与晶粒个数相关;试样在拉伸变形中出现45°方向的滑移剪切带和颈缩. 研究结果表明:多晶铜的对称应变循环可呈现出循环硬化和包辛格效应,导致包辛格效应的主要原因是晶间约束产生的残余应力. 在非对称应力循环载荷作用下,平均应力和应力幅值对多晶铜的棘轮行为有显著影响.     

基于动态区域规划的双模型车道线识别方法

为提高车道偏离预警以及前方车辆识别系统性能,提出一种基于动态区域规划的双模型结构化道路车道线检测方法。通过基于模板的腐蚀、膨胀处理改善了图像预处理效果。根据“微元”理论进行图像动态细化分区,对各区域局部独立识别,整体综合分析,最终利用直线和B-样条曲线双模型完成车道线拟合。 实车试验证明,直线/B-样条曲线双模型拟合,提高了算法对不同车道线的适应性。      

Galois环上的广义加性码

将Ζ2Ζ4-加性码推广到Galois环上,称为广义加性码.该文研究了Galois环上的广义加性码及其对偶码,给出了广义加性码及其对偶码的基本参数,生成矩阵及其标准型.此外,还研究了广义加性码的极小Lee距离的Singleton界.     

硅量子点表面掺氮的电子结构计算

本文在量子点表面掺入氮原子,用第一性原理方法模拟计算硅量子点（111）面上的电子结构.本文主要解决两个问题：（1）比较研究六种不同大小的量子点结构掺杂和未掺杂氮原子情况下的带隙宽度和电子态密度变化;（2）分别用广义梯度近似（GGA）和局域密度近似（LDA）两种不同的算法计算六种量子点结构的带隙宽度和态密度,并比较GGA和LDA算法的特点.计算结果发现：带隙随着量子点的尺度变小而展宽,这符合量子受限规律;在量子点表面掺杂氮原子会减小带隙宽度;重要的是发现LDA算法对局域态更加敏感.     

Carbocyanines — derivatives of nitrogen-containing heterocycles with bridging groups in the chromophore

Tetramethylene-2,2′-bis(1,3,3-trimethyl-(3H)-indolium),-3-ethylbenzothiazolium,-1-methyl-quinolinium, and-1-methyl-and-1-butylbenz[c,d]indolium salts were synthesized starting from them trimethinecyanines containing an ethylene bridging group in the α, α′-positions of the chromophore have been prepared. These compounds are converted to their analogs containing a vinylene group by the action of benzoquinones. In the case of thiacarbocyanines the effect of the indicated bridging groups on the conformation and protonation route of the carbocyanines has been studied. The chromaticity of the dyes has been investigated. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 94–102, January, 2008.