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基于 L-Lys-Ru(dcbpy)3(2+) 功能化多孔六棱柱状纳米棒的自增强电化学发光免疫传感器用于 CA15-3 的检测。

A self-enhanced electrochemiluminescence immunosensor based on L-Lys-Ru(dcbpy)3(2+) functionalized porous six arrises column nanorods for detection of CA15-3.

机构信息

Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China.

Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China.

出版信息

Biosens Bioelectron. 2015 Dec 15;74:924-30. doi: 10.1016/j.bios.2015.07.044. Epub 2015 Jul 23.

Abstract

In this work, a new manganese ions doped zinc oxide porous six arrises column nanorods was rapidly synthesized with L-Lys as the precipitating and capping agent (L-Lys/Mn-ZnONRs). The as-synthesized L-Lys/Mn-ZnONRs exhibited large specific surface area and high ferromagnetism, which could serve as excellent nanocarrier. Meanwhile, due to the outstanding conductivity and biocompatibility, platinum nanoparticles (PtNPs) were decorated on the surface of L-Lys/Mn-ZnONRs by Pt-N bond to form PtNPs/L-Lys/Mn-ZnONRs complexes. After that, the obtained complexes were used to immobilize abundant tris (4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium(II) dichloride (Ru(dcbpy)3(2+)) and detection antibody for construction of sandwiched electrochemiluminescence (ECL) immunosensor. Coincidentally, L-Lys not only acted as the precipitating and capping agent to control shape and size of L-Lys/Mn-ZnONRs, but also acted as a co-reactant of Ru(dcbpy)3(2+) to efficiently amplify the ECL signal. Importantly, L-Lys had free amino group which could link with Ru(dcbpy)3(2+)via amide bond to form a self-enhanced ECL complex. Through this way, the electron transfer path between luminophore and co-reactant reagent was shortened and the energy loss of luminophore was lessened. Consequently, the prepared ECL immunosensor showed excellent performance for the detection of carbohydrate antigen 15-3 in the range from 0.05 U/mL to 120 U/mL with a detection limit of 0.014 U/mL (S/N=3) and a correlation coefficient of R=0.9977. Moreover, the prepared ECL immunosensor had good stability, excellent selectivity and satisfactory reproducibility.

摘要

在这项工作中,我们以 L-赖氨酸(L-Lys)作为沉淀和封端剂(L-Lys/Mn-ZnONRs),快速合成了一种新型的锰离子掺杂氧化锌多孔六棱柱纳米棒。所合成的 L-Lys/Mn-ZnONRs 具有较大的比表面积和较高的铁磁性,可用作优异的纳米载体。同时,由于出色的导电性和生物相容性,铂纳米粒子(PtNPs)通过 Pt-N 键被修饰在 L-Lys/Mn-ZnONRs 表面,形成 PtNPs/L-Lys/Mn-ZnONRs 复合物。然后,将所得复合物用于固定丰富的三(4,4'-二羧酸-2,2'-联吡啶)钌(II)二氯化物(Ru(dcbpy)3(2+))和检测抗体,构建三明治型电化学发光(ECL)免疫传感器。碰巧的是,L-Lys 不仅作为沉淀和封端剂来控制 L-Lys/Mn-ZnONRs 的形状和尺寸,还作为 Ru(dcbpy)3(2+)的共反应物,有效地放大了 ECL 信号。重要的是,L-Lys 具有游离的氨基,可通过酰胺键与 Ru(dcbpy)3(2+)连接,形成自增强的 ECL 复合物。通过这种方式,缩短了发光体和共反应物之间的电子转移路径,减少了发光体的能量损失。因此,所制备的 ECL 免疫传感器在 0.05 U/mL 至 120 U/mL 的范围内对糖链抗原 15-3 的检测表现出优异的性能,检测限为 0.014 U/mL(S/N=3),相关系数为 R=0.9977。此外,所制备的 ECL 免疫传感器具有良好的稳定性、优异的选择性和令人满意的重现性。

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