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三(2,2'-联吡啶)钌(II)-氧化锆-全氟磺酸复合膜用作毛细管电泳的固态电化学发光检测器。

Tris(2,2'-bipyridyl)ruthenium(II)-zirconia-Nafion composite films applied as solid-state electrochemiluminescence detector for capillary electrophoresis.

作者信息

Ding Shou-Nian, Xu Jing-Juan, Chen Hong-Yuan

机构信息

The Key Lab of Analytical Chemistry for Life Science, Department of Chemistry, Nanjing University, Nanjing 210 093, China.

出版信息

Electrophoresis. 2005 May;26(9):1737-44. doi: 10.1002/elps.200410324.

Abstract

The major goal of this work was to develop a new solid-state electrochemiluminescence (ECL) detector suitable for capillary electrophoresis (CE). The detector was fabricated by coating a sol-gel derived zirconia (ZrO(2))-Nafion composite film on a graphite electrode, then the zirconia-Nafion modified electrode was immersed in tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3) (2+)) solution to immobilize this active chemiluminescence reagent. The voltammetric and ECL behaviors of the detector were investigated and optimized in tripropylamine solution. The ratio of 53% for zirconia in the zirconia-Nafion composite provided the highest luminescence intensity of immobilized Ru(bpy)(3) (2+). The ECL can maintain its stability very well in the phosphate solution in the period of 5-90 h when the solid-state ECL detector was immersed in the solution all the time. The optimum distance of capillary outlet to the solid-state ECL detector has been found to be ca. 50-80 microm for a 75 microm capillary. The effects of ionic strength and pH of ECL solution on peak height were investigated. The CE with solid-state ECL detector system was successfully used to detect tripropylamine, lidocaine, and proline. The detection limits (S/N = 3) were 5 x 10(-9) mol.L(-1) for tripropylamine, 1 x 10(-8) mol.L(-1) for lidocaine and 5 x 10(-6) mol.L(-1) for proline, and the linear ranges were from 1.0 x 10(-8) to 1.0 x 10(-5) mol.L(-1) for tripropylamine, 5.0 x 10(-7) mol.L(-1) to 1.0 x 10(-5) mol.L(-1) for lidocaine and 1.0 x 10(-5) to 1.0 x 10(-3) mol.L(-1) for proline, respectively.

摘要

这项工作的主要目标是开发一种适用于毛细管电泳(CE)的新型固态电化学发光(ECL)检测器。该检测器是通过在石墨电极上涂覆溶胶 - 凝胶衍生的氧化锆(ZrO₂)-Nafion复合膜制成的,然后将氧化锆 - Nafion修饰电极浸入三(2,2'-联吡啶)钌(II)(Ru(bpy)₃²⁺)溶液中以固定这种活性化学发光试剂。在三丙胺溶液中研究并优化了该检测器的伏安和ECL行为。氧化锆 - Nafion复合物中氧化锆含量为53%时,固定化Ru(bpy)₃²⁺的发光强度最高。当固态ECL检测器一直浸入磷酸盐溶液中时,在5 - 90小时内ECL能很好地保持其稳定性。对于内径75微米的毛细管,已发现毛细管出口到固态ECL检测器的最佳距离约为50 - 80微米。研究了ECL溶液的离子强度和pH对峰高的影响。带有固态ECL检测器系统的毛细管电泳成功用于检测三丙胺、利多卡因和脯氨酸。三丙胺的检测限(S/N = 3)为5×10⁻⁹ mol·L⁻¹,利多卡因为1×10⁻⁸ mol·L⁻¹,脯氨酸为5×10⁻⁶ mol·L⁻¹,线性范围分别为三丙胺1.0×10⁻⁸至1.0×10⁻⁵ mol·L⁻¹,利多卡因5.0×10⁻⁷至1.0×10⁻⁵ mol·L⁻¹,脯氨酸1.0×10⁻⁵至1.0×10⁻³ mol·L⁻¹。

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