Palonen Sami, Jussila Matti, Porras Simo P, Riekkola Marja-Liisa
Laboratory of Analytical Chemistry, Department of Chemistry, University of Helsinki, Finland.
Electrophoresis. 2004 Jan;25(2):344-54. doi: 10.1002/elps.200305756.
Nonaqueous capillary electrophoretic separations were performed under high electric field strengths (up to 2000 Vcm(-1)) in ethanolic background electrolyte solution and the contributions of different band broadening effects to plate height were evaluated. Under optimum conditions, increasing the field strength will provide faster separations and increased separation efficiency. Decrease in the separation efficiency at high field strengths was, however, observed in a previous study and now in the present paper an attempt is made to quantify various band broadening effects by applying a plate height model, which included the contributions of the injection plug length, diffusion, electromigration dispersion, Joule heating, analyte adsorption to the capillary wall, and detector slit aperture length. Of special interest were the contributions of Joule heating and analyte adsorption to the capillary wall. Poly(glycidylmethacrylate-co-N-vinylpyrrolidone)-coated fused-silica capillaries were used with internal diameters (ID) ranging from 30 to 75 microm. The separation efficiencies obtained experimentally were compared with the theoretically calculated efficiencies and fairly good agreement was observed for the 30 microm ID capillary. Relatively large deviation from the predictions of the model was found for the other capillary diameters especially at higher field strengths. The possible reasons for the deviation were discussed.
在乙醇背景电解质溶液中,于高电场强度(高达2000 Vcm⁻¹)下进行非水毛细管电泳分离,并评估了不同谱带展宽效应对塔板高度的贡献。在最佳条件下,提高电场强度可实现更快的分离并提高分离效率。然而,在先前的研究中观察到高电场强度下分离效率会降低,并且在本文中,现在尝试通过应用塔板高度模型来量化各种谱带展宽效应,该模型包括进样塞长度、扩散、电迁移扩散、焦耳热、分析物在毛细管壁上的吸附以及检测器狭缝孔径长度的贡献。特别令人感兴趣的是焦耳热和分析物在毛细管壁上的吸附的贡献。使用内径(ID)范围为30至75微米的聚(甲基丙烯酸缩水甘油酯 - 共 - N - 乙烯基吡咯烷酮)涂层熔融石英毛细管。将实验获得的分离效率与理论计算效率进行比较,对于内径为30微米的毛细管观察到了相当好的一致性。对于其他毛细管直径,特别是在较高电场强度下,发现与模型预测存在相对较大的偏差。讨论了偏差的可能原因。