Gold Nanoparticle-Induced Photocurrent Quenching and Recovery of Polymer Dots: Toward Signal-On Energy-Transfer-Based Photocathodic Bioanalysis of Telomerase Activity in Cell Extracts.

Energy transfer (ET) in photoelectrochemical (PEC) bioanalysis is usually generated between noble metal nanoparticles (NPs) and traditional inorganic quantum dots (QDs). Using the innovative polymer dot (Pdot)-involved ET, this work reports the first signal-on and cathodic PEC bioanalysis toward telomerase (TE) activity in cell extracts. Specifically, the sequential binding of capture DNA (cDNA), telomerase primer sequence (TS), and Au NP-labeled probe DNA (Au NP-pDNA) on the electrode would place the Au NPs in close proximity of the Pdots, leading to obvious quenching of the cathodic photocurrent. The subsequent extension of the TS by TE in the presence of deoxyribonucleoside triphosphates (dNTPs) would then release the Ag NP-pDNA from the electrode, leading to the recovery of the photocurrent. On the basis of the Au NP-induced photocurrent quenching and the recovery of Pdots, a sensitive biosensor could thus be developed by tracking the photocurrents to probe the TE activity. This strategy allows for signal-on and cathodic PEC bioanalysis of TE, which can be easily extended for numerous other targets of interest. We believe this work could offer a new perspective for the rational implementation of Pdot-involved ET for advanced PEC bioanalysis.

Binding-induced formation of DNAzyme on an Au@Ag nanoparticles/TiO2 nanorods electrode: Stimulating biocatalytic precipitation amplification for plasmonic photoelectrochemical bioanalysis.

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)/TiO2 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.

Semiconducting CuO Nanotubes: Synthesis, Characterization, and Bifunctional Photocathodic Enzymatic Bioanalysis.

This work reports the synthesis, characterization, and application of bifunctional semiconducting CuO nanotubes (NTs) electrode for innovative synergized cathodic photoelectrochemical (PEC) enzymatic bioanalysis. Specifically, CuO NTs electrode was fabricated by surface oxidation of the copper foil in an alkaline aqueous solution with (NH4)2S2O8 and then annealed in air at 200 °C. After the subsequent coupling with the model enzyme of xanthine oxidase (XOD), the resulted photocathodic enzyme biosensor exhibited good analytical performance of rapid response, high stability, and good sensitivity. Especially, due to the unique catalytic property of CuO toward H2O2, a novel enzymatic cascade design between biological catalyst (XOD as natural enzyme) and biomimetic catalyst (CuO as the peroxidase mimetics) was constructed, and the dual-catalyst system with special synergy effect could achieve the cathodic PEC guanine bioanalysis with enhanced efficiency. In the determination, the cathodic photocurrent was found to be proportional to the guanine concentration, which was different from the commonly observed O2-dependent suppression of the photocurrent. In all, such a bifunctional CuO NTs-based PEC bioassay format has not been reported. The success of this work can offer great chances for further development and implementation of novel CuO-based PEC bioanalytical systems. More importantly, the strategy proposed here could contribute to the development of an original prototype for general PEC enzymatic bioanalysis.

Hierarchical CuInS2-based heterostructure: Application for photocathodic bioanalysis of sarcosine.

In this study, on the basis of hierarchical CuInS2-based heterostructure, a novel cathodic photoelectrochemical (PEC) enzymatic bioanalysis of the sarcosine detection was reported. Specifically, heterostructured CuInS2/NiO/ITO photocathode was prepared and sarcosine oxidases (SOx) were integrated for the construction of the enzymatic biosensor. In the bioanalysis, the O2-dependent suppression of the cathodic photocurrent can be observed due to the competition between the as-fabricated O2-sensitive photocathode and the SOx-catalytic event toward O2 reduction. Based on the sarcosine-controlled O2 concentration, a novel photocathodic enzymatic biosensor could be realized for the sensitive and specific sarcosine detection. This work manifested the great potential of CuInS2-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 CuInS2-based heterostructured photocathodic enzymatic sensing.

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.

Ag nanoclusters could efficiently quench the photoresponse of CdS quantum dots for novel energy transfer-based photoelectrochemical bioanalysis.

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 1.0pM to 10nM and the detection limit was experimentally found to be of 0.3pM. This work presents a feasible signaling principle that could act as a common basis for general PEC bioanalysis development.

Sulfonation of ordered mesoporous carbon supported Pd catalysts for formic acid electrooxidation.

A novel supporting material containing benzenesulfonic acid (BSA) groups and ordered mesoporous carbons (OMCs) was first prepared by in situ radical polymerization of 4-styrenesulfonate and isoamyl nitrite under ambient conditions. Then, Pd nanoparticles were deposited on as-produced OMCs (f-OMCs) by the NaBH(4) reduction method. The structure and nature of the resulting composites were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and nitrogen adsorption-desorption. The results show that BSA groups are created and the texture and surface chemistry are altered, whereas the ordered porous structure is maintained. The electrocatalytic properties of the Pd/f-OMCs catalysts for formic acid oxidation (HCOOH) have been investigated by cyclic voltammetry and chronoamperometry methods, and excellent electrocatalytic activity can be observed.

Synthesis and electrochemical properties of chemically substituted LiMn2O4 prepared by a solution-based gel method.

Lithium manganese oxide, LiMn(2)O(4), and its substituted samples LiM(0.05)Mn(1.95)O(4) (M=Al, Co, and Zn) were first prepared by a cost-saving and effective new solution-based gel method using a mixture of acetate and ethanol as the chelating agent. The physical properties of the synthesized samples were investigated by thermogravimetry/differential thermal analysis, X-ray diffraction, and scanning electronic microscopy. The as-prepared powders were used as positive materials for a lithium-ion battery, whose charge/discharge properties and cycle performance were examined. The results revealed that all the substituted samples had better cycle performance than pure LiMn(2)O(4). Among these synthesized materials, the LiCo(0.05)Mn(1.95)O(4) sample had the best cycle performance. After 30 cycles, its capacity loss was only 3%. Therefore, cyclic voltammetry and electrochemical impedance spectroscopy were employed to characterize the reactions of Li ion insertion into and extraction from LiCo(0.05)Mn(1.95)O(4) electrodes.

Enhancement of the electrochemical properties of LiMn2O4 through Al3+ and F- co-substitution.

The cathode-active materials LiMn2O4, LiAl0.1Mn1.9O4, and LiAl0.1Mn1.9O3.9F0.1 were synthesized by a microwave-assisted sol-gel method. The influence of different doping elements on the structural and electrochemical properties of the as-prepared samples was investigated by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and electrochemical experiments. The results indicated that fluorine plays an important role in controlling the morphology, and the doped aluminum could enhance significantly the stability of spinel-type LiMn2O4. The initial discharge capacity of the Al3+ and F- co-substituted specimen reached 129.8 mA h/g and has a high capacity retention after 40 cycles. The outstanding electrochemical properties of LiAl0.1Mn1.9O3.9F0.1 make it a possible promising cathode material for lithium-ion batteries.

Preparation of novel nano-composite Ni(OH)2/USY material and its application for electrochemical capacitance storage.

A novel nano-composite material of Ni(OH)2/USY was prepared in our lab. This nanostructure creates electrochemical accessibility of electrolyte OH- ions to Ni(OH)2 thin layers and a fast diffusion rate within the redox phase.