Luminescence-Based Spectroelectrochemical Sensor for [Tc(dmpe)3]2+/+ (dmpe = 1,2-bis(dimethylphosphino)ethane) within a Charge-Selective Polymer Film

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• 作者：Sayandev Chatterjee ; Andrew S. Del Negro ; Matthew K. Edwards ; Samuel A. Bryan ; Necati Kaval ; Nebojsa Pantelic ; Laura K. Morris ; William R. Heineman ; Carl J. Seliskar
• 刊名：Analytical Chemistry
• 出版年：2011
• 出版时间：March 1, 2011
• 年：2011
• 卷：83
• 期：5
• 页码：1766-1772
• 全文大小：911K
• 年卷期：v.83,no.5(March 1, 2011)
• ISSN：1520-6882

文摘

A spectroelectrochemical sensor consisting of an indium tin oxide (ITO) optically transparent electrode (OTE) coated with a thin film of partially sulfonated polystyrene-blockpoly(ethylene-ran-butylene)-block-polystyrene (SSEBS) was developed for [Tc(dmpe)<sub>3sub>]<sup>+sup> (dmpe = 1,2-bis(dimethylphosphino)ethane). [Tc(dmpe)<sub>3sub>]<sup>+sup> was preconcentrated by ion-exchange into the SSEBS film after a 20 min exposure to aqueous [Tc(dmpe)<sub>3sub>]<sup>+sup> solution, resulting in a 14-fold increase in cathodic peak current compared to a bare OTE. Colorless [Tc(dmpe)<sub>3sub>]<sup>+sup> was reversibly oxidized to colored [Tc(dmpe)<sub>3sub>]<sup>2+sup> by cyclic voltammetry. Detection of [Tc(dmpe)<sub>3sub>]<sup>2+sup> was accomplished through emission spectroscopy by electrochemically oxidizing the complex from nonemissive [Tc(dmpe)<sub>3sub>]<sup>+sup> to emissive [Tc(dmpe)<sub>3sub>]<sup>2+sup>. The working principle of the sensor consisted of electrochemically cycling between nonemissive [Tc(dmpe)<sub>3sub>]<sup>+sup> and emissive [Tc(dmpe)<sub>3sub>]<sup>2+sup> and monitoring the modulated emission (位<sub>excsub> = 532 nm; 位<sub>emsub> = 660 nm). The sensor gave a linear response over the concentration range of 0.16鈭?40.0 渭M of [Tc(dmpe)<sub>3sub>]<sup>2+/+sup> in aqueous phase with a detection limit of 24 nM.