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用树枝状大分子包裹的纳米颗粒修饰氧化铟锡,以增强Ru(bpy)3(2+)/三丙胺的稳定电化学发光,同时保持氧化铟锡的光学透明度,用于基于电化学发光的灵敏分析。

Modification of indium tin oxide with dendrimer-encapsulated nanoparticles to provide enhanced stable electrochemiluminescence of Ru(bpy)3(2+)/tripropylamine while preserving optical transparency of indium tin oxide for sensitive electrochemiluminescence-based analyses.

作者信息

Kim Yeoju, Kim Joohoon

机构信息

Department of Chemistry, Research Institute for Basic Sciences, Kyung Hee University , 1 Hoegi-dong, Seoul 130-701, Republic of Korea.

出版信息

Anal Chem. 2014 Feb 4;86(3):1654-60. doi: 10.1021/ac403415m. Epub 2014 Jan 17.

Abstract

Here, we report highly enhanced stable electrogenerated chemiluminescence (ECL) of Ru(bpy)3(2+) (bpy = 2,2'-bipyridyl) with tripropylamine (TPrA) coreactant on indium tin oxide (ITO) electrodes modified with amine-terminated dendrimers encapsulating catalytic nanoparticles while maintaining optical transparency of ITO and feasibility of the modified ITOs to sensitive ECL-based assays. As model systems, we prepared Pt and Au dendrimer-encapsulated nanoparticles (DENs) using amine-terminated sixth-generation poly(amido amine) dendrimers and subsequently immobilized the DENs onto ITO surfaces via electrooxidative grafting of the terminal amines of dendrimers to the surfaces. The resulting DEN-modified ITOs preserved good optical transparency of ITO and exhibited highly catalyzed electrochemical oxidation of Ru(bpy)3(2+)/TPrA, leading to significantly increased ECL emission. Especially, the Pt DEN-modified ITO electrode provides negligible transmittance drop, i.e., only ∼1.99% over the entire visible region, and exhibited not only much enhanced (i.e., ∼213-fold increase compared to ECL obtained from bare ITO) but also stable ECL emission under consecutive potential scans from 0.00 to 1.10 V for 10 cycles, which allowed ∼329 times more sensitive ECL-based analysis of nicotine using the Pt DEN-modified ITO compared with the use of bare ITO.

摘要

在此,我们报道了在封装有催化纳米颗粒的胺端基树枝状大分子修饰的氧化铟锡(ITO)电极上,钌(Ⅱ)联吡啶配合物(Ru(bpy)₃²⁺,bpy = 2,2'-联吡啶)与三丙胺(TPrA)共反应剂之间实现了高度增强的稳定电致化学发光(ECL),同时保持了ITO的光学透明度以及修饰后的ITO用于基于ECL的灵敏检测的可行性。作为模型系统,我们使用胺端基的第六代聚酰胺-胺树枝状大分子制备了铂和金树枝状大分子封装的纳米颗粒(DENs),随后通过树枝状大分子末端胺的电氧化接枝将DENs固定在ITO表面。所得的DEN修饰的ITO保持了ITO良好的光学透明度,并表现出对Ru(bpy)₃²⁺/TPrA的高度催化电化学氧化,从而导致ECL发射显著增加。特别是,铂DEN修饰的ITO电极在整个可见光区域的透光率下降可忽略不计,即仅约1.99%,并且在从0.00至1.10 V进行10个循环的连续电位扫描下,不仅表现出大大增强的(即与从裸ITO获得的ECL相比增加了约213倍)而且稳定的ECL发射,这使得与使用裸ITO相比,使用铂DEN修饰的ITO对尼古丁进行基于ECL的分析灵敏度提高了约329倍。

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