Yi-Fan Ruan

Alkaline Phosphatase Tagged Antibodies on Gold Nanoparticles/TiO2 Nanotubes Electrode: A Plasmonic Strategy for Label-Free and Amplified Photoelectrochemical Immunoassay

This work reports a plasmonic strategy capable of label-free yet amplified photoelectrochemical (PEC) immunoassay for the sensitive and specific detection of model protein p53, an important transcription factor that regulates the cell cycle and functions as a tumor suppressor. Specifically, on the basis of Au nanoparticles (NPs) deposited on hierarchically ordered TiO2 nanotubes (NTs), a protein G molecular membrane was used for immobilization of alkaline phosphatase (ALP) conjugated anti-p53 (ALP-a-p53). Due to the immunological recognition between the receptor and target, the plasmonic charge separation from Au NPs to the conduction band of TiO2 NTs could be influenced greatly that originated from multiple factors. The degree of signal suppression is directly associated with the target concentration, so by monitoring the changes of the plasmonic photocurrent responding after the specific binding, a new plasmonic PEC immunoassay could be tailored for label-free and amplified detection. The operating principle of this study could be extended as a general protocol for numerous other targets of interest.

Simultaneous Photoelectrochemical Immunoassay of Dual Cardiac Markers Using Specific Enzyme Tags: A Proof of Principle for Multiplexed Bioanalysis

In this Letter, on the basis of the CdS quantum dots functionalized TiO2 nanotubes electrode, we proposed a simultaneous photoelectrochemical (PEC) immunoassay of dual cardiac markers using specific enzyme tags of alkaline phosphatase (ALP) and acetylcholine esterase (AChE). ALP and AChE were integrated into the PEC system through the sandwich immunobinding and could specifically catalyze the hydrolysis of ascorbic acid 2-phosphate (AAP) or the acetylthiocholine (ATC) to in situ generate ascorbic acid (AA) or thiocholine (TC) for sacrificial electron donating. These two enzymes were thus used to differentiate the signals of two cardiac targets in connection with the sandwich immunorecognition and PEC responses to the corresponding electron donors. This strategy demonstrates a proof of principle for the successful integration of dual enzyme tags with PEC immunoassay that can potentially provide a general format for multiplexed PEC bioanalysis.

Protein Binding Bends the Gold Nanoparticle Capped DNA Sequence: Toward Novel Energy-Transfer-Based Photoelectrochemical Protein Detection

In this work, we present a novel energy-transfer (ET)-based photoelectrochemical (PEC) probing of DNA-protein interactions, which associates intimately with many important intracellular processes in transcriptional regulatory networks. Specifically, Au nanoparticles (NPs) were confined onto the CdS quantum dots (QDs) functionalized PEC surface by the formation of duplex DNA, the subsequent binding of the TATA binding protein (TBP) and the resulting distortion of the Au NPs capped DNA sequence could adjust the interparticle distance and thereby modulate the PEC performance of CdS QDs through the ET process between the CdS QDs and Au NPs. Using the duplex DNA sequence as a rigid spacer, the relationship between the photocurrent quenching effect and the spacing distance was also studied and some experimental conditions were optimized, on the basis of which a novel ET-based PEC TBP biosensor was realized with high sensitivity and selectivity.

Quantum-dots-based photoelectrochemical bioanalysis highlighted with recent examples

Photoelectrochemical (PEC) bioanalysis is a newly developed methodology that provides an exquisite route for innovative biomolecular detection. Quantum dots (QDs) are semiconductor nanocrystals with unique photophysical properties that have attracted tremendous attentions among the analytical community. QDs-based PEC bioanalysis comprises an important research hotspot in the field of PEC bioanalysis due to its combined advantages and potentials. Currently, it has ignited increasing interests as demonstrated by increased research papers. This review aims to cover the most recent advances in this field. With the discussion of recent examples of QDs-PEC bioanalysis from the literatures, special emphasis will be placed on work reporting on fundamental advances in the signaling strategies of QDs-based PEC bioanalysis from 2013 to now. Future prospects in this field are also discussed.

Simultaneous photoelectrochemical and visualized immunoassay of β-human chorionic gonadotrophin.

Herein, on the basis of the alkaline phosphate (ALP) induced reaction, a simultaneous photoelectrochemical (PEC) and visualized immunoassay has been established for the detection of β-human chorionic gonadotrophin (β-HCG). Specifically, in the proposed system, ALP stimulated the oxidative hydrolyzing transformation of 5-bromo-4-chloro-3-indoyl phosphate (BCIP) to an indigo precipitation, generating an insulating layer that impeded the interfacial mass and electron transfer and thus the photocurrent production. Meanwhile, a visualized detection could be performed according to the change of color intensity. Upon proper experimental conditions, the protocol possessed a detection range of 0.5-1000IU/L with a detection limit of (0.20±0.011)IU/L toward β-HCG. With high sensitivity and specificity, this work presents the first general protocol for simultaneous PEC and visualized detection, which could be easily extended to addressing numerous other targets.

Bismuth Oxyiodide Couples with Glucose Oxidase: A Special Synergized Dual-Catalysis Mechanism for Photoelectrochemical Enzymatic Bioanalysis

On the basis of a special synergized dual-catalysis mechanism, this work reports the preparation of a BiOI-based heterojunction and its use for cathodic photoelectrochemical (PEC) oxidase biosensing, which, unexpectedly, revealed that hydrogen peroxide (H2O2) had a greater impact than dioxygen (O2). Specifically, the BiOI layer was in situ formed on the substrate through an impregnating hydroxylation method for the following coupling with the model enzyme of glucose oxidases (GOx). The constructed cathodic PEC enzyme sensor exhibited a good analytical performance of rapid response, high stability, and good selectivity. Especially, glucose-induced H2O2-controlled enhancement of the photocurrent was recorded rather than the commonly observed O2-dependent suppression of the signal. This interesting phenomenon was attributed to a special synergized dual-catalysis mechanism. Briefly, this study is expected to provide a new BiOI-based photocathode for general PEC bioanalysis development and to inspire more interest in the design and construction of a novel heterojunction for advanced photocathodic bioanalysis. More importantly, the mechanism revealed here would offer a totally different perspective for the use of a biomimetic catalyst in the design of future PEC enzymatic sensing and the understanding of relevant signaling routes as well as the implementation of innovative PEC devices.

Photoelectrochemical Bioanalysis Platform of Gold Nanoparticles Equipped Perovskite Bi4NbO8Cl

We have developed sensitive photoelectrochemical (PEC) detection of cysteine using the gold nanoparticles (Au NPs) equipped perovskite Bi4NbO8Cl heterostructure. The Bi4NbO8Cl was prepared by a solid-state reaction, and the Au NPs/Bi4NbO8Cl electrode was made through the electrostatic layer-by-layer self-assembly technique. The Au NPs/Bi4NbO8Cl electrode provided much enhanced photocurrent with a great increase compared to the bare Bi4NbO8Cl electrode and allowed for the plasmon-enhanced PEC detection of cysteine with good performance. It demonstrated rapid response, high stability, wide linear detection range and certain selectivity, implying its great promise in its application. Therefore, the Au NPs/Bi4NbO8Cl heterostructure has provided a promising platform for the development of PEC bioanalysis. More generally, these findings offered an insight into the exploitation of perovskite materials for PEC bioanalytical purposes.

Nanochannels Photoelectrochemical Biosensor

Nanochannels have brought new opportunities for biosensor development. Herein, we present the novel concept of a nanochannels photoelectrochemical (PEC) biosensor based on the integration of a unique CuxO-nanopyramid-islands (NPIs) photocathode, an anodic aluminum oxide (AAO) membrane, and alkaline phosphatase (ALP) catalytic chemistry. The CuxO-NPIs photocathode possesses good performance, and further assembly with AAO yields a designed architecture composed of vertically aligned, highly ordered nanoarrays on top of the CuxO-NPIs film. After biocatalytic precipitation (BCP) was stimulated within the channels, the biosensor was used for the successful detection of ALP activity. This study has not only provided a novel paradigm for an unconventional nanochannels PEC biosensor, which can be used for general bioanalytical purposes, but also indicated that the new concept of nanochannel-semiconductor heterostructures is a step toward innovative biomedical applications.

Organic Photo‐Electrochemical Transistor‐Based Biosensor: A Proof‐of‐Concept Study toward Highly Sensitive DNA Detection

Organic bioelectronics have shown promising applications for various sensing purposes due to their significant advantages in term of high flexibility, portability, easy fabrication, and biocompatibility. Here, a new type of organic device, organic photo-electrochemical transistor (OPECT), is reported, which is the combination of an organic electrochemical transistor and a photo-electrochemical gate electrode modified with CdS quantum dots (QDs). Thanks to the inherent amplification function of the transistor, the OPECT-based biosensor exhibits much higher sensitivity than that of a traditional biosensor. The sensing mechanism of the OPECT is attributed to the charge transfer between the photosensitive semiconductor CdS QDs and the gate electrode. In an OPECT-based DNA sensor, target DNA is labeled with Au nanoparticles (NPs) and captured on the gate electrode, which can influence the charge transfer on the gate caused by the exciton-plasmon interactions between CdS QDs and Au NPs. Consequently, a highly sensitive and selective DNA sensor with a detection limit of around 1 × 10-15 m is realized. It is expected that OPECTs can be developed as a high-performance platform for numerous biological detections in the future.