Zhang Jing, Devaramani Samrat, Shan Duoliang, Lu Xiaoquan
Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province, College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou, Gansu, 730070, China.
Anal Bioanal Chem. 2016 Oct;408(25):7155-63. doi: 10.1007/s00216-016-9655-0. Epub 2016 Jun 17.
The cathodic electrochemiluminescence (ECL) behavior of meso-tetra(4-sulfonatophenyl)porphyrin (TSPP) with potassium peroxydisulfate (K2S2O8) as the coreactant in aqueous solution with strong and stable emission was exploited to determine Cu(2+) down to nanomolar concentration. Two possible reaction mechanisms have been proposed to understand the generation of ECL by the TSPP/K2S2O8 system. The effects of the concentration of TSPP and K2S2O8, pH of the medium, and scan rate on the ECL intensity were studied in detail. The ECL intensity was efficiently quenched by trace amounts of Cu(2+). This phenomenon was used to develop a new method, which can offer rapid, reliable, and selective detection of Cu(2+). Under the optimum conditions, plots of the ECL of the TSPP/K2S2O8 system versus the concentration of Cu(2+) are linear in the range of 5 to 160 nM with a detection limit of 1.56 nM (S/N = 3). The proposed ECL sensor was successfully applied for analysis of tap and river water samples. It is anticipated that TSPP could be a new class of promising luminescent agent for ECL sensors. Graphical Abstract A two-step cathodic elelctrochemiluminescence (ECL) behavior of TSPP/K2S2O8 system in the aqueous solution and Cu(2+) determination using the same.
以过二硫酸钾(K₂S₂O₈)为共反应剂,研究了中位四(4 - 磺酸基苯基)卟啉(TSPP)在水溶液中的阴极电化学发光(ECL)行为,该体系具有强而稳定的发射,可用于测定低至纳摩尔浓度的Cu(2+)。为理解TSPP/K₂S₂O₈体系产生ECL的过程,提出了两种可能的反应机制。详细研究了TSPP和K₂S₂O₈的浓度、介质pH值以及扫描速率对ECL强度的影响。痕量的Cu(2+)能有效猝灭ECL强度。利用这一现象开发了一种新方法,可实现对Cu(2+)的快速、可靠且选择性的检测。在最佳条件下,TSPP/K₂S₂O₈体系的ECL强度与Cu(2+)浓度的校准曲线在5至160 nM范围内呈线性,检测限为1.56 nM(S/N = 3)。所提出的ECL传感器成功应用于自来水和河水样品的分析。预计TSPP可能成为一类用于ECL传感器的新型有前景的发光剂。图形摘要:TSPP/K₂S₂O₈体系在水溶液中的两步阴极电化学发光(ECL)行为及基于此的Cu(2+)测定