College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China.
Luminescence. 2011 Sep-Oct;26(5):319-23. doi: 10.1002/bio.1231. Epub 2010 Aug 25.
On the basis of an europium (III)-doped Prussian blue analog film modifying platinum electrode as the working electrode, a Ru(bpy)₃²⁺-based electrochemiluminescence (ECL) assay coupled with capillary electrophoresis has been first established for the determination of ketotifen fumarate (KTF). Analytes were injected onto a separation capillary of 50 cm length (50 μm i.d., 360 μm o.d.) by electrokinetic injection for 10 s at 10 kV. Parameters related to the separation and detection were discussed and optimized. It was proved that 15 mM phosphate buffer at pH 8.0 could achieve the most favorable resolution, and the highest sensitivity of detection was obtained using the detection potential at 1.25 V and 5 mM Ru(bpy)₃²⁺ in 100 mM phosphate buffer at pH 8.0 in the detection reservoir. Under the optimized conditions, the ECL intensity was in proportion to KTF concentration over the range from 3.0 × 10⁻⁸ to 5.0 × 10⁻⁶ g mL⁻¹ with a detection limit of 2.1 × 10⁻⁸ g mL⁻¹ (3σ). The relative standard deviations of the ECL intensity and the migration time were 0.95 and 0.26%, respectively. The developed method was successfully applied to determine KTF contents in pharmaceuticals and human urine with recoveries between 99.5 and 107.0%.
基于修饰铂电极的铕（III）掺杂普鲁士蓝类似物薄膜作为工作电极，首次建立了一种基于 Ru(bpy)₃²⁺的电化学发光（ECL）分析与毛细管电泳相结合的方法，用于测定富马酸酮替芬（KTF）。通过电动进样，在 10 kV 下将分析物注入 50 cm 长（50 µm id，360 µm od）的分离毛细管中 10 s。讨论并优化了与分离和检测相关的参数。结果证明，在 pH 8.0 的 15 mM 磷酸盐缓冲液中可以实现最佳的分辨率，而在检测池中使用检测电位为 1.25 V 和 5 mM Ru(bpy)₃²⁺、pH 8.0 的 100 mM 磷酸盐缓冲液可以获得最高的检测灵敏度。在优化条件下，ECL 强度与 KTF 浓度在 3.0 × 10⁻⁸ 至 5.0 × 10⁻⁶ g·mL⁻¹范围内呈比例关系，检测限为 2.1 × 10⁻⁸ g·mL⁻¹（3σ）。ECL 强度和迁移时间的相对标准偏差分别为 0.95%和 0.26%。该方法成功应用于测定药物和人尿中的 KTF 含量，回收率在 99.5%至 107.0%之间。
