Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.
Anal Chem. 2011 Mar 1;83(5):1766-72. doi: 10.1021/ac1030368. Epub 2011 Feb 4.
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)(3) (dmpe = 1,2-bis(dimethylphosphino)ethane). Tc(dmpe)(3) was preconcentrated by ion-exchange into the SSEBS film after a 20 min exposure to aqueous Tc(dmpe)(3) solution, resulting in a 14-fold increase in cathodic peak current compared to a bare OTE. Colorless Tc(dmpe)(3) was reversibly oxidized to colored Tc(dmpe)(3) by cyclic voltammetry. Detection of Tc(dmpe)(3) was accomplished through emission spectroscopy by electrochemically oxidizing the complex from nonemissive Tc(dmpe)(3) to emissive Tc(dmpe)(3). The working principle of the sensor consisted of electrochemically cycling between nonemissive Tc(dmpe)(3) and emissive Tc(dmpe)(3) and monitoring the modulated emission (λ(exc) = 532 nm; λ(em) = 660 nm). The sensor gave a linear response over the concentration range of 0.16-340.0 μM of Tc(dmpe)(3) in aqueous phase with a detection limit of 24 nM.
一种由掺锡氧化铟（ITO）光学透明电极（OTE）涂覆一层部分磺化聚苯乙烯-嵌段-聚（乙烯-ran-丁烯）-嵌段-聚苯乙烯（SSEBS）的光谱电化学传感器被开发出来，用于[Tc(dmpe)(3)]+（dmpe = 1,2-双（二甲基膦基）乙烷）。[Tc(dmpe)(3)]+通过离子交换在暴露于含[Tc(dmpe)(3)]+的水溶液 20 分钟后被预浓缩到 SSEBS 膜中，与裸 OTE 相比，阴极峰电流增加了 14 倍。无色[Tc(dmpe)(3)]+通过循环伏安法可逆地被氧化为有色[Tc(dmpe)(3)]2+。通过电化学将配合物从非发光的[Tc(dmpe)(3)]+氧化为发光的[Tc(dmpe)(3)]2+，通过发射光谱检测[Tc(dmpe)(3)]2+。传感器的工作原理包括在非发光的[Tc(dmpe)(3)]+和发光的[Tc(dmpe)(3)]2+之间电化学循环，并监测调制的发射（λ(exc) = 532nm；λ(em) = 660nm）。该传感器在水溶液中[Tc(dmpe)(3)]2+/+的浓度范围为 0.16-340.0 μM 时给出线性响应，检测限为 24 nM。
