Tu Chuanhong, Lee Hian Kee
Department of Chemistry, National University of Singapore, Singapore.
J Chromatogr A. 2002 Aug 9;966(1-2):205-12. doi: 10.1016/s0021-9673(02)00744-6.
A capillary zone electrophoresis (CZE) method was established to determine low concentration nitrate which was online preconcentrated with chloride-induced leading-type sample self-stacking for seawater samples. The sample self-stacking was based on transient isotachophoresis in which chloride served as leading ion, and dihydrogenphosphate in the background electrolyte (0.1 M phosphate) as the terminating one. Due to the small mobility difference between nitrate and chloride, the isotachophoresis time was so long that nitrate could not separate from the rear sharp boundary between chloride and the background electrolyte (BGE) when it migrated to the detection window. A zwitterionic surfactant, 3-(N,N-dimethyldodecylammonio)propane sulfonate was added to the BGE to enlarge the mobility difference for its selective interaction with anions. Thus, a highly conductive sample could be injected in a large volume with about fourfold sensitivity enhancement compared to that of field amplification sample stacking in which nitrate was dissolved in pure water. The relative standard deviations (n=5) of migration time, peak area, peak height were 0.1, 3.0, 1.5%, respectively. The limit of detection (S/N=3) for nitrate was 35 microg/l in seawater samples with relatively low concentration BGE (0.1 M sodium phosphate, pH 6.2). The overall procedure consisting of online preconcentration and separation was as simple as routine CZE except for a slightly longer sample injection time (3-4 min).
建立了一种毛细管区带电泳(CZE)方法,用于测定低浓度硝酸盐,该方法采用氯化物诱导的前导型样品自堆积在线预富集海水样品中的硝酸盐。样品自堆积基于瞬态等速电泳,其中氯化物作为前导离子,背景电解质(0.1 M磷酸盐)中的磷酸二氢根作为终止离子。由于硝酸盐和氯化物之间的迁移率差异较小,等速电泳时间过长,以至于硝酸盐迁移到检测窗口时无法与氯化物和背景电解质(BGE)之间的后锐边界分离。向BGE中加入两性离子表面活性剂3-(N,N-二甲基十二烷基铵)丙烷磺酸盐,以扩大其与阴离子选择性相互作用的迁移率差异。因此,与硝酸盐溶解在纯水中的场放大样品堆积相比,可以大体积进样高导电性样品,灵敏度提高约四倍。迁移时间、峰面积、峰高的相对标准偏差(n=5)分别为0.1%、3.0%、1.5%。在相对低浓度BGE(0.1 M磷酸钠,pH 6.2)的海水样品中,硝酸盐的检测限(S/N=3)为35 μg/l。除进样时间稍长(3-~4分钟)外,由在线预富集和分离组成的整个过程与常规CZE一样简单。