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夹心型电化学发光肽生物传感器,基于中空磁性自增强纳米片,用于早期癌症预后标志物的检测。

Sandwiched Electrochemiluminescent Peptide Biosensor for the Detection of Prognostic Indicator in Early-Stage Cancer Based on Hollow, Magnetic, and Self-Enhanced Nanosheets.

机构信息

Key Laboratory of Luminescent and Real-TimeAnalytical Chemistry, Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, P. R. China.

出版信息

Small. 2015 Aug 12;11(30):3703-9. doi: 10.1002/smll.201500321. Epub 2015 Apr 2.

Abstract

Currently, peptide-based protein-recognition has been recognized as an effective and promising approach for protein assays. However, sandwiched peptide-based biosensor with high sensitivity and low background has not been proposed before. Herein, a sandwiched electrochemiluminescence (ECL) peptide-based biosensor is constructed for Cyclin A(2) (CA2), a prognostic indicator in early stage of multiple cancers, based on nanosheets with hollow, magnetic, and ECL self-enhanced properties. First, hollow and magnetic manganese oxide nanocrystals (H-Mn(3)O(4)) are synthesized using triblock copolymeric micelles with core-shell-corona architecture as templates. Then, polyethyleneimine (PEI) and the composite of platinum nanoparticles and tris (4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium (II) (PtNPs-Ru) are immobilized on H-Mn(3)O(4) to form H-Mn(3)O(4) -PEI-PtNPs-Ru nanocomposite, in which PEI as coreactant can effectively enhance the luminous efficiency and PtNPs as nanochannels can greatly accelerate the electron transfer. Finally, due to the coordination between Eu(3+) and carboxyl, the obtained H-Mn(3)O(4) -PEI-PtNPs-Ru aggregates locally to form sheet-like nanostructures ((H-Mn(3)O(4) -PEI-PtNPs-Ru)(n) -Eu(3+)), by which the luminous efficiency is further increased. Based on the nanosheets and two designed peptides, a sandwiched ECL biosensor, using palladium nanocages synthesized through galvanic replacement reaction as substrate, is proposed for CA2 with a linear range from 0.001 to 100 ng mL(-1) and a detection limit of 0.3 pg mL(-1).

摘要

目前,基于肽的蛋白质识别已被认为是一种有效且有前途的蛋白质分析方法。然而,以前尚未提出具有高灵敏度和低背景的夹心肽基生物传感器。在此,基于具有中空、磁性和 ECL 自增强特性的纳米片,构建了一种夹心电化学发光(ECL)肽基生物传感器,用于检测多种癌症早期的预后标志物 Cyclin A(2)(CA2)。首先,使用具有核壳冠结构的三嵌段共聚物胶束作为模板合成中空和磁性氧化锰纳米晶体(H-Mn(3)O(4))。然后,将聚乙烯亚胺(PEI)和铂纳米粒子与三(4,4'-二羧酸-2,2'-联吡啶)钌(II)(PtNPs-Ru)的复合物固定在 H-Mn(3)O(4)上,形成 H-Mn(3)O(4)-PEI-PtNPs-Ru 纳米复合材料,其中 PEI 作为共反应物可以有效提高发光效率,PtNPs 作为纳米通道可以极大地加速电子转移。最后,由于 Eu(3+)和羧基之间的配位,得到的 H-Mn(3)O(4)-PEI-PtNPs-Ru 聚集体局部形成片状纳米结构((H-Mn(3)O(4)-PEI-PtNPs-Ru)(n)-Eu(3+)),从而进一步提高了发光效率。基于纳米片和两个设计的肽,使用通过电置换反应合成的钯纳米笼作为基底,构建了一种夹心 ECL 生物传感器,用于 CA2 的检测,线性范围为 0.001 至 100ng mL(-1),检测限为 0.3pg mL(-1)。

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