Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine

Nanocatalysts are a promising alternative to natural enzymes as the signal labels of electrochemical biosensors. However, the surface modification of nanocatalysts and sensor electrodes with recognition elements and blockers may form a barrier to direct electron transfer, thus limiting the applicati...

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Main Authors: Xiaohua Ma, Dehua Deng, Ning Xia, Yuanqiang Hao, Lin Liu
Format: Article
Language:English
Published: MDPI AG 2021-07-01
Series:Nanomaterials
Subjects:
Online Access:https://www.mdpi.com/2079-4991/11/7/1757
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author Xiaohua Ma
Dehua Deng
Ning Xia
Yuanqiang Hao
Lin Liu
author_facet Xiaohua Ma
Dehua Deng
Ning Xia
Yuanqiang Hao
Lin Liu
author_sort Xiaohua Ma
collection DOAJ
description Nanocatalysts are a promising alternative to natural enzymes as the signal labels of electrochemical biosensors. However, the surface modification of nanocatalysts and sensor electrodes with recognition elements and blockers may form a barrier to direct electron transfer, thus limiting the application of nanocatalysts in electrochemical immunoassays. Electron mediators can accelerate the electron transfer between nanocatalysts and electrodes. Nevertheless, it is hard to simultaneously achieve fast electron exchange between nanocatalysts and redox mediators as well as substrates. This work presents a scheme for the design of electrochemical immunosensors with nanocatalysts as signal labels, in which pyrroloquinoline quinone (PQQ) is the redox-active center of the nanocatalyst. PQQ was decorated on the surface of carbon nanotubes to catalyze the electrochemical oxidation of tris(2-carboxyethyl)phosphine (TCEP) with ferrocenylmethanol (FcM) as the electron mediator. With prostate-specific antigen (PSA) as the model analyte, the detection limit of the sandwich-type immunosensor was found to be 5 pg/mL. The keys to success for this scheme are the slow chemical reaction between TCEP and ferricinum ions, and the high turnover frequency between ferricinum ions, PQQ. and TCEP. This work should be valuable for designing of novel nanolabels and nanocatalytic schemes for electrochemical biosensors.
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spelling doaj.art-e164e680c33242e68554e90f8dd8598e2023-11-22T04:33:27ZengMDPI AGNanomaterials2079-49912021-07-01117175710.3390/nano11071757Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphineXiaohua Ma0Dehua Deng1Ning Xia2Yuanqiang Hao3Lin Liu4Henan Key Laboratory of Biomolecular Recognition and Sensing, Shangqiu Normal University, Shangqiu 476000, ChinaCollege of Chemistry and Chemical Engineering, Anyang Normal University, Anyang 455000, ChinaCollege of Chemistry and Chemical Engineering, Anyang Normal University, Anyang 455000, ChinaHenan Key Laboratory of Biomolecular Recognition and Sensing, Shangqiu Normal University, Shangqiu 476000, ChinaHenan Key Laboratory of Biomolecular Recognition and Sensing, Shangqiu Normal University, Shangqiu 476000, ChinaNanocatalysts are a promising alternative to natural enzymes as the signal labels of electrochemical biosensors. However, the surface modification of nanocatalysts and sensor electrodes with recognition elements and blockers may form a barrier to direct electron transfer, thus limiting the application of nanocatalysts in electrochemical immunoassays. Electron mediators can accelerate the electron transfer between nanocatalysts and electrodes. Nevertheless, it is hard to simultaneously achieve fast electron exchange between nanocatalysts and redox mediators as well as substrates. This work presents a scheme for the design of electrochemical immunosensors with nanocatalysts as signal labels, in which pyrroloquinoline quinone (PQQ) is the redox-active center of the nanocatalyst. PQQ was decorated on the surface of carbon nanotubes to catalyze the electrochemical oxidation of tris(2-carboxyethyl)phosphine (TCEP) with ferrocenylmethanol (FcM) as the electron mediator. With prostate-specific antigen (PSA) as the model analyte, the detection limit of the sandwich-type immunosensor was found to be 5 pg/mL. The keys to success for this scheme are the slow chemical reaction between TCEP and ferricinum ions, and the high turnover frequency between ferricinum ions, PQQ. and TCEP. This work should be valuable for designing of novel nanolabels and nanocatalytic schemes for electrochemical biosensors.https://www.mdpi.com/2079-4991/11/7/1757electrochemical immunosensornanocatalystredox cyclingquinone
spellingShingle Xiaohua Ma
Dehua Deng
Ning Xia
Yuanqiang Hao
Lin Liu
Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine
Nanomaterials
electrochemical immunosensor
nanocatalyst
redox cycling
quinone
title Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine
title_full Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine
title_fullStr Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine
title_full_unstemmed Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine
title_short Electrochemical Immunosensors with PQQ-Decorated Carbon Nanotubes as Signal Labels for Electrocatalytic Oxidation of Tris(2-carboxyethyl)phosphine
title_sort electrochemical immunosensors with pqq decorated carbon nanotubes as signal labels for electrocatalytic oxidation of tris 2 carboxyethyl phosphine
topic electrochemical immunosensor
nanocatalyst
redox cycling
quinone
url https://www.mdpi.com/2079-4991/11/7/1757
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AT dehuadeng electrochemicalimmunosensorswithpqqdecoratedcarbonnanotubesassignallabelsforelectrocatalyticoxidationoftris2carboxyethylphosphine
AT ningxia electrochemicalimmunosensorswithpqqdecoratedcarbonnanotubesassignallabelsforelectrocatalyticoxidationoftris2carboxyethylphosphine
AT yuanqianghao electrochemicalimmunosensorswithpqqdecoratedcarbonnanotubesassignallabelsforelectrocatalyticoxidationoftris2carboxyethylphosphine
AT linliu electrochemicalimmunosensorswithpqqdecoratedcarbonnanotubesassignallabelsforelectrocatalyticoxidationoftris2carboxyethylphosphine