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首页> 外文期刊>Electrophoresis: The Official Journal of the International Electrophoresis Society >Sample stacking in CZE using dynamic thermal junctions II: analytes with high dpKa/dT crossing a single thermal junction in a BGE with low dpH/dT.
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Sample stacking in CZE using dynamic thermal junctions II: analytes with high dpKa/dT crossing a single thermal junction in a BGE with low dpH/dT.

机译：使用动态热结在CZE中进行样品堆叠II：高dpKa / dT的分析物穿过低dpH / dT的BGE中的单个热结。

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摘要

In a previous work [M. Mandaji, et al., this issue] a sample stacking method was theoretically modeled and experimentally demonstrated for analytes with low dpK(a)/dT (analytes carrying carboxylic groups) and BGEs with high dpH/dT (high pH-temperature-coefficients). In that work, buffer pH was modulated with temperature, inducing electrophoretic mobility changes in the analytes. In the present work, the opposite conditions are studied and tested, i.e. analytes with high dpK(a)/dT and BGEs that exhibit low dpH/dT. It is well known that organic bases such as amines, imidazoles, and benzimidazoles exhibit high dpK(a)/dT. Temperature variations induce instantaneous changes on the basicity of these and other basic groups. Therefore, the electrophoretic velocity of some analytes changes abruptly when temperature variations are applied along the capillary. This is true only if BGE pH remains constant or if it changes in the opposite direction of pK(a) of the analyte. The presence of hot and cold sections along the capillary also affects local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band stacking efficacy was also taken into account in the theoretical model presented. Finally, this stacking method is demonstrated for lysine partially derivatized with naphthalene-2,3-dicarboxaldehyde. In this case, the amino group of the lateral chain was left underivatized and only the alpha amino group was derivatized. Therefore, the basicity of the lateral amino group, and consequently the electrophoretic mobility, was modulated with temperature while the pH of the buffer used remained unchanged.
机译：在以前的工作中[M. Mandaji等人，[本期]对dpK（a）/ dT低（带有羧基的分析物）和dpH / dT高（pH-温度系数高）的BGE的分析物进行了理论建模和实验证明。在这项工作中，缓冲液的pH值随温度调节，从而导致分析物的电泳迁移率发生变化。在目前的工作中，研究和测试了相反的条件，即具有高dpK（a）/ dT的分析物和具有低dpH / dT的BGE。众所周知，有机碱如胺，咪唑和苯并咪唑显示出高的dpK（a）/ dT。温度变化引起这些基团和其他基团的碱性的瞬时变化。因此，当沿毛细管施加温度变化时，某些分析物的电泳速度会突然改变。仅当BGE pH值保持恒定或沿被分析物pK（a）的相反方向变化时，这才成立。沿毛细管的热区和冷区的存在也会影响局部粘度，电导率和电场强度。在给出的理论模型中也考虑了这些变量对电泳速度和谱带堆叠效率的影响。最终，证明了用萘-2,3-二二甲醛部分衍生的赖氨酸的这种堆积方法。在这种情况下，侧链的氨基未衍生化，仅α氨基被衍生。因此，侧氨基的碱性以及因此的电泳迁移率随温度而调节，而所用缓冲液的pH保持不变。

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