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Enzymatic biosensors have been valuable bioanalytical devices for analysis of diverse targets in disease diagnosis, biological and biomedical research, etc. Photoelectrochemical (PEC) bioanalysis is a recently emerged method that promptly becoming a subject of new research interests due to its attractive potential for future bioanalysis with high sensitivity and specificity. PEC enzymatic biosensors integrate the inherent sensitivities of PEC bioanalysis and the selectivity of enzymes and thus share their both advantages. Currently, PEC enzymatic biosensors have become a hot topic of significant research and the recent impetus has grown rapidly as demonstrated by increased research papers. Given the pace of advances in this area, this review will make a thorough discussion and survey on the fundamentals, sensing strategies, applications and the state of the art in PEC enzymatic biosensors, followed by future prospects based on our own opinions. We hope this work could provide an accessible introduction to PEC enzymatic biosensors for any scientist. [ABSTRACT FROM AUTHOR]

Abstract: In this work, we firstly enunciated the presence of synergy effect between the electron and energy transfer in an electrochemiluminescence (ECL) system involving the CdS NCs and Au NPs, based on which an amplified ECL biosensor was constructed for sensitive detection of DNA–protein interactions. Specifically, Au NPs modified on electrode, following by assembled probe DNA. Then the modified GCE was hybridized with SiO2@CdS/DNA conjugates. With DNA duplex as a rigid spacer, Au NPs could not only accelerate the electron transfer but also produce the surface plasma resonance upon excited ECL of CdS NCs. However, the enhanced ECL could be greatly suppressed by the binding of target protein. The prepared biosensor possesses excellent analytical performance with the linear range of target protein from 0.015 to 150nM. [Copyright &y& Elsevier]

Abstract: On the basis of aptamer-based rolling circle amplification (RCA) and magnetic beads (MBs), a highly sensitive electrochemical method was developed for the determination of Ochratoxin A (OTA). Initially, an amino-modified capture DNA was immobilized onto MBs for the following hybridization with an OTA aptamer and a phosphate labeled padlock DNA. In the presence of OTA, the aptamer would dissociate from the bioconjugate, and the padlock DNA would subsequently hybridize with the capture DNA to form a circular template with the aid of the T4 ligase. Next, capture DNA would act as primer to initiate a linear RCA reaction and hence generate a long tandem repeated sequences by phi29 DNA polymerase and dNTPs. Then, two quantum dots (QDs) labeled DNA probes were tagged on the resulted RCA product to indicate the OTA recognition event by electrochemical readout. This strategy, based on the novel design of OTA-mediated DNA circularization, the combination of RCA and double signal probes introduction, could detect OTA down to the level of 0.2pgmL−1 with a dynamic range spanning more than 4 orders of magnitude. The proposed approach is tested to determine OTA in red wines and shows good application potential in real samples. [Copyright &y& Elsevier]

The field of organic photoelectrochemical transistor (OPECT) is newly emerged, with increasing efforts attempting to utilize its properties in biological sensing. Advanced materials with new physicochemical properties have proven important to this end. Herein, we report a metal-organic polymers-gated OPECT biosensing exemplified by CuⅠ-arylacetylide polymers (CuAs)-modulated poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) channel. Both the photoelectrochemical properties and gating capability of CuAs are explored and optimized for high-efficacy photogating. Morever, based on its inherent structure, the specific reaction between CuAs and sulfur ions (S2−) is revealed and S2−-mediated microRNA-21 detection is realized by linking with nucleic acid amplification and alkaline phosphatase catalytic chemistry. This work introduces metal-organic polymers as gating materials for OPECT biosensing. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: A novel and simple method for preparing cadmium sulfide nanoparticles (CdS NPs) functionalized colloidal carbon particles (CPs) has been successfully developed by in situ growing abundant CdS NPs on the surfaces of monodisperse carbon particles (CdS/CPs). The obtained CdS/CPs conjugates as signal amplification labels were further used for the ultrasensitive determination of thrombin. The CdS/CPs conjugates were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV–visible absorption spectrum (UV). The protein electrical detection involves a dual binding event, based on thrombin linked to the CdS/CPs tags and glass surface by the specific aptamer–protein affinity interactions and a succedent electrochemical stripping transduction. Owing to the high-content CdS NPs on carbon particles, this assay allowed a desirable detection limit of 6.0×10−17 M, which was 1000 times lower than that of only using CdS NPs as labels in the control experiments. This protocol exhibited excellent selectivity against these common proteins such as bovine plasma albumin, lysozyme and hemoglobin. The signal amplification approach proposed here provides a facile, cost-effective method for the ultrasensitive determination of thrombin in the practical samples. [Copyright &y& Elsevier]

DNA intercalation has increasingly been studied for various scenario implementations due to the diverse functions of DNA/intercalators. Nascent organic photoelectrochemical transistor (OPECT) biosensing taking place in organic electronics and photoelectrochemical bioanalysis represents a promising technological frontier in the arena. In this work, we first devise DNA intercalation-enabled OPECT for miRNA detection with a superior gain up to 17100. Intercalation of [Ru(bpy) 2 dppz]2+ within the miRNA-initiated hybrid chain reaction (HCR)-derived duplex DNA is realized for producing anodic photocurrent upon light stimulation, causing the corresponding target-dependent alternation in gate voltage (V G) and hence the modulated channel current (I DS) of poly (3,4-ethylenedioxythiophene) doped with poly (styrene sulfonate) (PEDOT:PSS) under specific drain voltage (V DS) for quantitative miRNA-21 analysis, which shows a wide linear relationship and a low detection limit of 5.5 × 10−15 mol L−1. This study features the DNA intercalation-enabled organic electronics with superior gain and is envisaged to attract more attention to explore DNA adducts for innovative bioelectronics and biosensing, given the diverse DNA binders with multiple functions. [Display omitted] [ABSTRACT FROM AUTHOR]

Liposomal photoelectrochemical (PEC) bioanalysis holds enormous potential for future sensitive PEC bioanalysis. With tyrosinase (Tyr) and TiO 2 as representative enzyme and electrode, respectively, this communication reports the elegant use of Tyr-loaded liposomes (TLL) toward in situ sensitization of the electrode and thereby the realization of ultrasensitive PEC immunoassay. Specifically, Tyr-encapsulated and detection antibody-functionalized liposomes were first prepared and used as the signal probe. The subsequent sandwich immunobinding could confine the functional liposomes, which were then lysed with surfactant to release the encapsulated Tyr. The free Tyr could then initiate the transformation of tyrosine to dopa, the latter could bind with the undercoordinated Ti sites, forming the stable dopa–Ti charge transfer complex and thus generating enhanced anodic photocurrent under visible light for signaling. Since different semiconductors and enzymes may be adapted into this format, this work is expected to stimulate more interest in the enzyme-induced activation of semiconductors for advanced liposomal PEC bioanalysis. • Tyrosinase-encapsulated liposomes was fabricated and used as labels. • In situ sensitization of the TiO 2 electrode was realized by tyrosinase catalytic chemistry. • The system exhibited good performance for PEC immunoassay application. [ABSTRACT FROM AUTHOR]

Photoelectrochemical (PEC) DNA bioanalysis has been drawing more attention in recent years due to the advantages of PEC technique and the vital importance of DNA biomolecules. DNAzymes are unique catalytic nucleic acid molecules that are capable of catalyzing specific biochemical reactions. Using the target-binding-induced conformation change of hairpin DNA probe to hemin/G-quadruplex-based DNAzyme and a plasmonic Au@Ag nanoparticles (NPs)/TiO 2 nanorods (NRs)/fluorine-doped tin oxide (FTO) heterostructured photoelectrode, this work reported a novel and sensitive PEC DNA analysis on the basis of a DNAzyme-stimulated biocatalytic precipitation (BCP) strategy. In such a design, the BCP-induced decrease of plasmonic photocurrent can be related to the target-responsive formation of DNAzymes and thus be monitored to assay the target DNA from 0.1 and 100 nM. In brief, with a plasmonic photoelectrode and a hairpin probe, this work reported a general plasmonic DNAzyme-based PEC DNA analysis, which could also be easily extended to aptasensing toward numerous targets of interest. • Au@Ag nanoparticles/TiO 2 nanorods heterostructure electrode was fabricated. • Binding-induced formation of DNAzyme was allowed on the electrode. • Biocatalytic precipitation amplification was stimulated for plasmonic photoelectrochemical bioanalysis. [ABSTRACT FROM AUTHOR]

In this study, on the basis of hierarchical CuInS 2 -based heterostructure, a novel cathodic photoelectrochemical (PEC) enzymatic bioanalysis of the sarcosine detection was reported. Specifically, heterostructured CuInS 2 /NiO/ITO photocathode was prepared and sarcosine oxidases (SOx) were integrated for the construction of the enzymatic biosensor. In the bioanalysis, the O 2 -dependent suppression of the cathodic photocurrent can be observed due to the competition between the as-fabricated O 2 -sensitive photocathode and the SOx-catalytic event toward O 2 reduction. Based on the sarcosine-controlled O 2 concentration, a novel photocathodic enzymatic biosensor could be realized for the sensitive and specific sarcosine detection. This work manifested the great potential of CuInS 2 -based heterostructure as a novel platform for future PEC bioanalytical development and also a PEC method for sarcosine detection, which could be easily extended to numerous other enzymatic systems and to our knowledge has not been reported. This work is expected to stimulate more interest in the design and implementation of numerous CuInS 2 -based heterostructured photocathodic enzymatic sensing. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

This work reports the use of compositionally heterogeneous asymmetric Ag@Au core–satellite nanoassembly functionalized with DNA sequence as unique signaling nanoprobes for the realization of new energy-transfer-based photoelectrochemical (PEC) immunoassay of prostate- specific antigen (PSA). Specifically, the Ag@Au asymmetric core–satellite nanoassemblies (Ag@Au ACS) were fabricated on a two-dimensional glass substrate by a modified controlled assembly technique, and then functionalized with DNA sequences containing PSA aptamers as signaling nanoprobes. Then, the sandwich complexing between the PSA, its antibodies, and the signaling nanoprobes was performed on a CdS QDs modified indium tin oxide (ITO) electrode. The single stranded DNA can server as a facile mediator that place the Ag@Au ACS in proximity of CdS QDs, stimulating the interparticle exciton–plasmon interactions between Ag@Au ACS and CdS QDs and thus quenching the excitonic states in the latter. Since the damping effect is closely related to the target concentration, a novel energy-transfer-based PEC bioanalysis could be achieved for the sensitive and specific PSA assay. The developed biosensor displayed a linear range from 1.0×10 −11 g mL −1 to 1.0×10 −7 g mL −1 and the detection limit was experimentally found to be of 0.3×10 –13 g mL −1 . This strategy used the Ag@Au ACS-DNA signaling nanoprobes and overcame the deficiency of short operating distance of the energy transfer process for feasible PEC immunoassay. More significantly, it provided a way to couple the plasmonic properties of the Ag NPs and Au NPs in a single PEC bioanalytical system. We expected this work could inspire more interests and further investigations on the advanced engineering of the core–satellite or other judiciously designed nanostructures for new PEC bioanalytical uses with novel properties. [ABSTRACT FROM AUTHOR]

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 0.5–1000 IU/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. [ABSTRACT FROM AUTHOR]

Herein the influence of ultrasmall Ag nanoclusters (Ag NCs) against CdS quantum dots (QDs) in a photoelectrochemical (PEC) nanosystem was exploited for the first time, based on which a novel PEC bioanalysis was successfully developed via the efficient quenching effect of Ag NCs against the CdS QDs. In a model system, DNA assay was achieved by using molecular beacon (MB) probes anchored on a CdS QDs modified electrode, and the MB probes contain two segments that can hybridize with both target DNA sequence and the label of DNA encapsulated Ag NCs. After the MB probe was unfolded by the target DNA sequence, the labels of oligonucleotide encapsulated Ag NCs would be brought in close proximity to the CdS QDs electrode surface, and efficient photocurrent quenching of QDs could be resulted from an energy transfer process that originated from NCs. Thus, by monitoring the attenuation in the photocurrent signal, an elegant and sensitive PEC DNA bioanalysis could be accomplished. The developed biosensor displayed a linear range from 1.0 pM to 10 nM and the detection limit was experimentally found to be of 0.3 pM. This work presents a feasible signaling principle that could act as a common basis for general PEC bioanalysis development. [ABSTRACT FROM AUTHOR]

Innovative optoelectronics are expected to play more important role in clinical diagnosis. In this study, on the basis of sensitive gating effect by in situ enzymatic functionalization of semiconductors, a novel organic photoelectrochemical transistor (OPECT) detection of serum alkaline phosphatase (ALP) level was demonstrated. Specifically, the OPECT detection operates upon the ALP-catalyzed hydrolysis of sodium thiophosphate to yield hydrogen sulfide (H 2 S), which could in situ generate CdS on the TiO 2 electrode in the presence of Cd2+ cations. Correlated to the ALP level, the CdS directly formed on and interfacing with the TiO 2 could sensitively gating the poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) channel, allowing unique optoelectronic detection of serum ALP level with a linear range from 0.005 to 15 U L−1 and a detection limit corresponding to 0.0012 U L−1 (S/N = 3). This study offers not only an optoelectronic method for detection of serum ALP level, but also a perspective for unique OPECT gating and application. Moreover, the general catalytic abilities of enzymes to produce functional species and their rich interactions with various gate substrates further provide great space for futuristic OPECT detection in enzyme-associated diseases. [Display omitted] [ABSTRACT FROM AUTHOR]

Metal-organic framework (MOF) derivatives with unique physicochemical and electronic properties have seen a tremendous growth in diverse applications. Organic optobioelectronics have long been pursued in modern electronics for next-generation bio-relevant implementations. The intersection of these two disciplines could be an appealing way to pursue better performance of materials and devices. Herein this work reports the exploration of MOF derivatives and its ionic modulation for gating organic photoelectrochemical transistor (OPECT) biosensing. In the representative system of poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) gated by zeolitic-imidazolate-framework (ZIF)-8-derived Cd x Zn 1-x S, a high current gain could be achieved at zero gate bias. In connection to a CuO nanoparticle-labeled sandwich immunoassay, acidolysis-triggered Cu2+-induced ionic modulation of the system results into a good performance toward human IgG with a low limit of detection of 0.003 pg/mL. This work features the MOF derivative-gated organic electronics and is expected to inspire more interest to explore various MOF derivative electronics with unknown possibilities, considering the diversity of MOF derivatives. [Display omitted] [ABSTRACT FROM AUTHOR]

Photon-enabled bioelectronics has long been pursued in modern electronics due to their non-contact, remote-control, and even self-powered function interfacing the biological world with semiconductor devices. The debuting organic photoelectrochemical transistor (OPECT) relies on the photovoltage generated by the semiconductors to modulate the channel conductance, which enables light-fueled operation at zero gate bias. Inspired by the insulating nature of macrobiomolecules and surface capacitance mechanism, herein we demonstrate the biological regulation of the surface capacitance towards new OPECT biodetection, which was exemplified by a CdS quantum dots/TiO 2 nanotubes photoanode accommodating hybridization chain reaction (HCR) amplification with the target of biomarker miRNA-17. Formation of the non-conducting DNA layer from the miRNA-17-oriented HCR could decrease the surface capacitance and increase the corresponding fractional potential drop, shifting the transfer curve horizontally to higher gate voltage and thus producing different drain currents. The OPECT biosensor exhibited a linear relationship with the miRNA-17 concentration on the logarithmic axis in the range from 1 p m. to 10 μ m with a detection limit of 1 p m. This work not only represented a generic methodology of miRNA detection, but also provided a universal mechanism for the operation of advanced OPECT bioanalytics. [Display omitted] [ABSTRACT FROM AUTHOR]

Heart-type fatty acid binding protein (H-FABP) has been regarded as a promising biomarker for early diagnosis of acute myocardial infarction (AMI). Developing fast and reliable method for H-FABP detection is still highly desirable but challenging. Herein, an ascorbic acid (AA)-mediated organic photoelectrochemical transistor (OPECT) sensing strategy was reported for the detection of H-FABP in phosphate buffer saline (PBS) solution and human serum. A primary antibody/H-FABP/secondary antibody-Au NPs-alkaline phosphatase (ALP) sandwich immunorecognition structure was constructed. The modified ALP could catalytically convert ascorbic acid-2-phosphate to AA, which was then analyzed by OPECT. As a result, the AA-mediated OPECT sensing strategy realized highly sensitive detection of H-FABP with a detection limit of 3.23 × 10−14 g/mL which is two orders of magnitude lower than that of PEC method. Under optimal experimental conditions, H-FABP concentration could be obtained in ∼90 min. Importantly, the analysis of H-FABP was resistant to the interference from immunoglobulin G, bovine serum albumin, cysteine, AA and human serum. The proposed AA-mediated OPECT sensing strategy provides a simple, fast, and accurate way for H-FABP detection in AMI suspected patients. • Ascorbic acid-mediated OPECT sensing strategy was developed. • Selective and rapid detection of H-FABP was realized. • Enhanced sensitivity compared with traditional PEC technique. • Sensing mechanism of proposed strategy was demonstrated. [ABSTRACT FROM AUTHOR]

Solid-state nanochannels have great potentials in the vibrant field of photoelectrochemical (PEC) bioanalysis. This work herein demonstrates the innovative use of DNA-decorated nanoporous anodic alumina (NAA) nanochannels for sensitive PEC bioanalysis of telomerase (TE) activity. Specifically, telomerase primer sequences (TS) were initially immobilized within the NAA nanochannels and then extended by TE in the presence of deoxyribonucleoside triphosphates (dNTPs). The as formed single-strand DNA was then directed to hybrid with many partially matched single-strand assisting DNA (aDNA), leading to the formation of multiple DNAzymes by the unmatched parts and the subsequent DNAzyme-stimulated biocatalytic precipitation (BCP) within the nanochannels. Because the inhibited signals of the photoelectrode could be correlated with TE-enabled TS extension, an innovative nanochannels PEC bioanalysis could be realized for probing TE activity. This work features the ingenious use of DNA-associated nanochannels for PEC bioanalysis of TE activity. Given the versatile functions of DNA molecules, the extension of this strategy easily allows for addressing numerous other targets of interest. Also, we envision this work could inspire more interest for the further development of nanochannels PEC bioanalysis. • An innovative PEC bioanalysis of telomerase activity was proposed based on solid-state nanochannels. • The AgIn 5 S 8 /TiO 2 /ITO photoelectrode exhibited evident photocurrent response and high stability. • Target-induced formation of multiple DNAzymes could evidently amplify the PEC detection signal. • This strategy could be extended easily for building nanochannels PEC bioanalysis toward other targets of interest. [ABSTRACT FROM AUTHOR]

In this report, enhanced organic−inorganic heterojunction of polypyrrole@Bi 2 WO 6 was fabricated and applied for sensitive photoelectrochemical (PEC) immunoassay of creatine kinase-MB (CK-MB). Specifically, heterostructured polypyrrole@Bi 2 WO 6 photoelectrode was prepared and sandwich immunorecognition were integrated for the CK-MB immunoassay. In the detection, with the aid of alkaline phosphate (ALP)-induced biocatalytic precipitation (BCP), the precipitation-dependent suppression of the photocurrent can be recorded due to the impediment of the interfacial mass and electron transfer. On the basis of target-controlled BCP formation, a novel PEC immunoassay could be developed for the sensitive and specific CK-MB detection. This work manifested the great potential of polypyrrole@Bi 2 WO 6 heterojunction as a novel platform for PEC bioanalysis development and also a PEC method for CK-MB detection. This work is expected to stimulate more interest in the design and implementation of numerous other organic−inorganic heterojunction for advanced PEC bioanalysis development. • Organic−inorganic heterojunction of polypyrrole@Bi 2 WO 6 was fabricated. • Sandwich immunorecognition was directed on the heterojunction electrode. • Photoelectrochemical immunoassay of creatine kinase-MB was realized. [ABSTRACT FROM AUTHOR]