A rapid and sensitive colorimetric sensor for hypochlorite detection based on polyvinylpyrrolidone-stabilized gold nanoparticles.

It is important to develop simple and effective approaches for hypochlorite (OCl-) detection at trace levels due to its widespread use as a disinfectant especially for water treatments including drinking water. In this work, a simple, facile colorimetric sensor for the sensitive determination of hypochlorite was developed based on the oxidation of cysteine by OCl-, a process that prohibits the cysteine-triggered aggregation of Au nanoparticles (AuNPs) stabilized by polyvinylpyrrolidone. With this strategy, the concentration of OCl- could be detected with the naked eye and/or ultraviolet-visible spectroscopy, and the limit of detection for OCl- was 1.0 µM and 250 nM, respectively. Additionally, the proposed method shows excellent anti-interference capability against many other interfering ions and real water sample applicability.

Tungsten-oxygen bond pre-introduced VO2(B) nanoribbons enable fast and stable zinc ion storage ability.

The tunnel structure of the bronze phase vanadium dioxide (VO2(B)) can be used as the zinc ion storage active sites. However, the intense charge repulsion of divalent Zn2+ causes a sluggish reaction kinetics in the tunnel VO2(B). Here, a tungsten-oxygen bond pre-introduced (TOBI) approach is proposed to modulate the tunnel structure of VO2(B). The VO2(B) cathodes with TOBI of 0.5 at% to 3.0 at% have been controllably synthesized by a simple hydrothermal method. The results from structural analysis uncover that the pre-introduced W6+ replaces the V4+ in VO2(B) to form WO6 octahedra. Benefiting from the rapid diffusion kinetics, enhanced structural stability and improved conductivity enabled by the TOBI, the optimal VO2(B) nanoribbons with 1.5 at% shows a high reversible capacity of 265 mAh g-1, a high rate-performance of up-to 10 A g-1 and a long cycling stability of 2000 cycles. Moreover, a pseudo-capacitive dominated Zn2+ intercalation/de-intercalation behavior is solidly determined by the electrochemical kinetics testing and structural characterizations. This TOBI method is referential for developing other multivalent ion battery cathodes with outstanding performances.

Free-standing electrochemical biosensor for carcinoembryonic antigen detection based on highly stable and flexible conducting polypyrrole nanocomposite.

A flexible free-standing electrochemical biosensor to detect carcinoembryonic antigen (CEA) is described based on a conducting polypyrrole (PPy) nanocomposite film electrode. The conducting PPy composite was constructed by the sandwiched structure formed by PPy doped with pentaerythritol ethoxylate (PEE) and 2-naphthalene sulfonate (2-NS-PPy) separately via electropolymerization. Gold nanoparticles (AuNPs) were fixed on the PPy composite film by electrodeposition and then connected to CEA aptamer through self-assembly to construct a free-standing electrochemical biosensor breaking away from additional soft substrates and current collector. This PPy composite film-based electrochemical biosensor exhibits satisfying sensing performance for CEA detection, with a linear range from 10-10 g/mL to 10-6 g/mL and a detection limit of 0.033 ng/mL, good specificity and long-term sensing stability (96.8% of the original signal after 15 days). The biosensor also presents acceptable reproducibility with 1.7% relative standard deviation. Moreover, this electrochemical biosensor owns the deformation stability that could bear various deformations (twisting, folding, and knotting) without affecting device's sensing performance. It can even maintain 99.4% of the original signal under 25% strain deformation. Due to the superior sensing performance, high stability (mechanical deformation and long-term storage), and flexibility, this free-standing electrochemical biosensor proves huge potential in application of flexible and wearable electronics.

Electrochemical sensing interfaces based on hierarchically architectured zwitterionic peptides for ultralow fouling detection of alpha fetoprotein in serum.

Herein, an electrochemical sensing platform based on zwitterionic peptide with a hierarchical structure was constructed for ultralow fouling and highly sensitive protein quantification. Through the combination of CPPPPEKEKEKEK and CPPPPEKEKEK peptides, hierarchical antifouling peptide brushes were formed and exhibited excellent antifouling property, which can be further modified with alpha fetoprotein (AFP) aptamer to achieve highly sensitive detection of AFP. The hierarchical peptide brush-based sensor system achieved an AFP quantification range from 1.0 fg mL-1 to 1.0 ng mL-1, with a very low limit of detection as low as 0.59 fg mL-1. In addition, due to the superior antifouling property of the newly designed hierarchical peptide brushes, the electrochemical biosensor supported the quantification of AFP in solutions with a high concentration of nonspecific proteins without sacrifice in sensitivity. It is worth noting that the constructed antifouling biosensor ensured quantitative recruitment of AFP in clinical serum samples with acceptable accuracy when compared with the commonly used method in the hospital. The strategy of constructing sensing interfaces based on designed hierarchical peptide brushes provided an effective way to develop biosensors with both excellent antifouling capability and high sensitivity.

Electrochemical aptasensor based on conductive supramolecular polymer hydrogels for thrombin detection with high selectivity.

Herein, we synthesized a kind of conductive supramolecular polymer hydrogel (CSPH) based on polyaniline (PANI) which can not only improve the conductivity but also promote antifouling performance of the aptasensor for the specific recruitment of thrombin (TB) from complex samples. With the electrochemical copolymerization of aniline (AN) and 3-aminophenylboronic acid (ABA) on glassy carbon electrode (GCE), the electrode was then inserted into the polyvinyl alcohol (PVA) solution to obtain robust CSPH through boric acid groups incorporated onto PANI to cause gelation of PVA solution, owing to the hydrophilicity of CSPH and nearly electrical neutrality, the modified electrode is antifouling without integration of other antifouling materials. A sandwich-type electrochemical aptasensor was constructed on the CSPH based electrode interfaces. Thrombin aptamer 1 (TBA1) were modified on the CSPH through amide bond, and thrombin aptamer 2 modified magnetic nanoparticles (MNP-TBA2) are used as signal amplification probes, the aptasensor has good sensitivity with a linear range from 1 pmol/L to 10 nmol/L and has a detection limit down to 0.64 pmol/L. The strategy of utilizing eletropolymerization of CSPH films to undergo highly selective thrombin recognition is, of course, readily extended to a broad range of targets in the real samples, and the recovery was ranging from 95.2% to 106.3% and RSDs varying from 2.3% to 4.5%.

A nanocomposite consisting of MnO2 nanoflowers and the conducting polymer PEDOT for highly sensitive amperometric detection of paracetamol.

An electrochemical sensor for paracetamol is described that consists of a glassy carbon electrode (GCE) that was modified with the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with MnO2 nanoflowers. The hydrothermally synthesized MnO2 nanoflowers possess a large surface area and can be doped into PEDOT through electrochemical deposition to form a conducting polymer nanocomposite. The nanoflowers are shown to be uniformly distributed within the nanocomposite as revealed by elemental mapping analysis. The nanocomposite displays excellent catalytic activity toward the electrochemical oxidation of paracetamol. The modified GCE, best operated at a working potential of around 0.37 V (vs. SCE) has a linear response in 0.06 to 435 µM paracetamol concentration range and a very low limit of detection (31 nM at a signal-to-noise ratio of 3). The sensor exhibits excellent reproducibility and stability, and satisfying accuracy for paracetamol detection in pharmaceutical samples. Graphical abstract A highly sensitive electrochemical sensor capable of detecting paracetamol with a limit of detection down to 31 nM was developed based on MnO2 nanoflowers doped conducting polymer PEDOT.

Electrochemical Aptasensor for Ultralow Fouling Cancer Cell Quantification in Complex Biological Media Based on Designed Branched Peptides.

The rapid, convenient, and selective assaying of clinical targets directly in complex biological media brings with it the potential to revolutionize diagnostics. One major hurdle to impact is retention of selectivity and a tight control of nonspecific surface interactions or biofouling. We report herein, the construction of an antifouling interface through the covalent attachment of designed branched zwitterionic peptides onto electrodeposited polyaniline film. The antifouling capability of the designed branched peptide significantly outperforms that of the commonly used PEG and linear peptides. The interfaces modified with branched peptides are exceptionally effective in reducing a nonspecific protein and cell adsorption, as verified by electrochemical and fluorescent characterization. The derived sensors with mucin1 protein (MUC1) aptamer as the recognition element detect MUC1-positive MCF-7 breast cancer cells in human serum with high sensitivity and selectivity. The linear response range of the cytosensor for the MCF-7 cell is from 50 to 106 cells/mL, with a limit of detection as low as 20 cells/mL. More importantly, the assaying performances remain unchanged in human serum owing to the presence of branched antifouling peptide, indicating feasibility of the cytosensor for practical cancer cell quantification in complex samples.

High-activity Fe3O4 nanozyme as signal amplifier: A simple, low-cost but efficient strategy for ultrasensitive photoelectrochemical immunoassay.

Sensitive but with simple, inexpensive detection of disease-related biomarkers in real biological samples is of quite necessity for early diagnosis and disease surveillance. We herein first introduced high-activity Fe3O4 nanozyme as signal amplifier to develop an ultrasensitive photoelectrochemical (PEC) immunoassay, which meanwhile has the distinct merits of both simplicity and low cost compared with previously reported enzyme-labeling PEC immunoassays. In the proposal, to illustrate and describe the PEC platform, prostate-specific antigen (PSA, Ag) was used as a target model. Specifically, ZnO nanorods (ZnO-NRs) grown vertically on a bare indium-tin oxide (ITO) electrode was deposited with ZnIn2S4 nanocrystals, producing ZnIn2S4/ZnO-NRs/ITO photoelectrode as the PEC matrix to modify capture PSA antibody (Ab1). Histidine-modified Fe3O4 (his-Fe3O4) nanozyme as signal amplifier was linked with signal PSA antibody (Ab2) to form his-Fe3O4@Ab2 conjugate, and was anchored through specific sandwich immunoreaction. The labeling his-Fe3O4 nanozyme acted as a peroxidase to induce the generation of the insoluble and insulating precipitation, resulting in an evident decrease in the photocurrent signal. On account of combined effects of high catalytic efficiency of the his-Fe3O4 nanozyme and excellent PEC properties of the ZnIn2S4/ZnO-NRs/ITO photoelectrode, ultralow detection limit of 18 fg/mL for target Ag detection was achieved. Besides, as high-activity his-Fe3O4 nanozyme has substituted natural enzyme as signal amplifier, simplicity and low cost of the PEC immunoassay was realized.

Universal Design of Selectivity-Enhanced Photoelectrochemical Enzyme Sensor: Integrating Photoanode with Biocathode.

Previous work on photoelectrochemical (PEC) biosensors has demonstrated that the photoanode-based type possesses satisfying sensitivity, because photoanode utilize electrons as the majority charge carriers and a distinct photocurrent can be generated when electron donors are furnished. However, as hole-oxidation reaction occurs at the photoanode interface, the photoanode-based PEC sensor has inferior anti-interference capacity to reductive substances coexisting in the biological sample, leading to a challenged selectivity. Herein, a universal design on selectivity-enhanced PEC enzyme sensor was proposed by integrating a photoanode with a biocathode. Specifically, the CuInS2 sensitization layer and ZnS passivation layer were deposited in sequence on the TiO2 film modified indium-tin oxide (ITO) electrode mainly by successive ionic layer adsorption and reaction (SILAR) means, forming the hybrid ZnS/CuInS2/TiO2/ITO photoanode. A carbon fiber paper (CFP) electrode was modified with biocatalysts of enzymes via the assistance of chitosan (CS) to fabricate the biocathode. Utilizing glucose oxidase (GOx) and horserdish peroxidase (HRP) as biocatalysts, a selectivity-enhanced PEC sensor for glucose was developed. The PEC sensing platform integrating photoanode with biocathode not only inherits distinct photocurrent of the photoanode-based sensor but also possesses enhanced selectivity, because just the biocathode was incubated in the biological sample and there is no interaction between the photoanode and coexisting reductive substances.

Hierarchical Heterostructure of ZnO@TiO2 Hollow Spheres for Highly Efficient Photocatalytic Hydrogen Evolution.

The rational design and preparation of hierarchical nanoarchitectures are critical for enhanced photocatalytic hydrogen evolution reaction (HER). Herein, well-integrated hollow ZnO@TiO2 heterojunctions were obtained by a simple hydrothermal method. This unique hierarchical heterostructure not only caused multiple reflections which enhances the light absorption but also improved the lifetime and transfer of photogenerated charge carriers due to the potential difference generated on the ZnO-TiO2 interface. As a result, compared to bare ZnO and TiO2, the ZnO@TiO2 composite photocatalyst exhibited higher hydrogen production rated up to 0.152 mmol h-1 g-1 under simulated solar light. In addition, highly repeated photostability was also observed on the ZnO@TiO2 composite photocatalyst even after a continuous test for 30 h. It is expected that this low-cost, nontoxic, and readily available ZnO@TiO2 catalyst could exhibit promising potential in photocatalytic H2 to meet the future fuel needs.

Bioinspired Design of Strong, Tough, and Highly Conductive Polyol-Polypyrrole Composites for Flexible Electronics.

Inspired by the dynamic network structure of animal dermis, we have designed and synthesized a series of polyol-polypyrrole (polyol-PPy) composites. Polyols and polypyrrole are cross-linked by hydrogen bonding and electrostatic interactions to form a dynamic network, which helps to dissipate destructive energy. We have found a clear correlation between the mechanical properties of polyol-PPy composites and the polyols structure. Particularly, the PEE-PPy film shows both high strength and flexibility, leading to a remarkable tensile toughness comparable to cocoon silk. The combination of outstanding strength, ductility, and conductivity enables polyol-PPy composites (especially PEE-PPy) as potential electronic materials for making flexible electronics.

Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors.

We report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline-polyvinyl alcohol hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochemical capacitance (928 F g(-1) ). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm(-2) and 153 F g(-1) ) and a high energy density of 13.6 Wh kg(-1) , superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mechanical folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics.

Amperometric biosensor for hydrogen peroxide based on direct electrocatalysis by hemoglobin immobilized on gold nanoparticles/1,6-diaminohexane modified glassy carbon electrode.

A facile strategy of an amperometric biosensor for hydrogen peroxide based on the direct electrocatalysis of hemoglobin (Hb) immobilized on gold nanoparticles (GNPs)/1,6-diaminohexane (DAH) modified glassy carbon electrode (GCE) has been described. A uniform monolayer film of DAH was initially covalently bound on a GCE surface by virtue of the electrooxidation of one amino group of DAH, and another amino group was modified with GNPs and Hb, successively. The fabrication process was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The proposed biosensor exhibited an effective and fast catalytic response to the reduction of H2O2 with good reproducibility and stability. A linear relationship existed between the catalytic current and the H2O2 concentration in the range of 1.5x10(-6) to 2.1x10(-3) M with a correlation coefficient of 0.998 (n=24). The detection limit (S/N=3) was 8.8x10(-7) M.

The first dinuclear copper(II) and zinc(II) complexes containing novel Bis-TACN: syntheses, structures, and DNA cleavage activities.

Two novel binuclear complexes [Cu(2)(L)].(ClO(4))(2) (1) and [Zn(2)(L)].(ClO(4))(2) (2) were synthesized and crystallographically characterized {L = 1(4),5(4)-dimethyl-1(2),5(2)-dihydroxy-1(1,3),5(1,3)-dibenzene-3(1,4),7(1,4)-di-1,4,7-triazacyclononane}. The cation [Cu(2)(L)](2+) structure of 1 is similar to that of [Zn(2)(L)](2+) of 2. The central ion is bridged by the di-phenoxo of L and lies in a close to perfect square pyramidal geometry. 1 and 2 crystallize in the triclinic space group P1. The two complexes effectively promote the cleavage of plasmid DNA in the presence of activating agents at physiological pH and temperature. The pseudo-Michaelis-Menten kinetic parameters k(cat) = 1.61 h(-1), K(m) = 1.35 x 10(-5) M for complex 1 in the presence of mercaptoethanol; k(cat) = 2.48 h(-1), K(m) = 5.5 x 10(-5)M for complex 2 in the presence of hydrogen peroxide were obtained. The mechanism of plasmid DNA cleavage was studied by adding standard radical scavengers. DNA cleavage reaction by the binuclear Zn(II)/H(2)O(2) system is a hydrolytic mechanism.

A mediator-free amperometric hydrogen peroxide biosensor based on HRP immobilized on a nano-Au/poly 2,6-pyridinediamine-coated electrode.

A mediator-free amperometric hydrogen peroxide biosensor was prepared by immobilizing horseradish peroxidase (HRP) enzyme on colloidal Au modified platinum (Pt) wire electrode, which was modified by poly 2,6-pyridinediamine (pPA). The modified process was characterized by electrochemical impedance spectroscopy (EIS), and the electrochemical characteristics of the biosensor were studied by cyclic voltammetry, linear sweep voltammetry and chronoamperometry. The biosensor displayed an excellent electrocatalytical response to reduction of H(2)O(2) without the aid of an electron mediator, the linear range was 4.2 x 10(-7)-1.5 x 10(-3) mol/L (r = 0.9977), with a detection limit of 1.4 x 10(-7) mol/L. Moreover, the performance and factors influencing the resulted biosensor were studied in detail. The studied biosensor exhibited permselectivity, good stability and good fabrication reproducibility.

Amperometric hydrogen peroxide biosensor based on the immobilization of HRP on nano-Au/Thi/poly (p-aminobenzene sulfonic acid)-modified glassy carbon electrode.

A novel hydrogen peroxide biosensor was fabricated for the determination of H(2)O(2). The precursor film was first electropolymerized on the glassy carbon electrode with p-aminobenzene sulfonic acid (p-ABSA) by cyclic voltammetry (CV). Then thionine (Thi) was adsorbed to the film to form a composite membrane, which yielded an interface containing amine groups to assemble gold nanoparticles (nano-Au) layer for immobilization of horseradish peroxidase (HRP). The electrochemical characteristics of the biosensor were studied by CV and chronoamperometry. The factors influencing the performance of the resulting biosensor were studied in detail. The biosensor responded to H(2)O(2) in the linear range from 2.6 x 10(-6) mol/L to 8.8 x 10(-3) mol/L with a detection limit of 6.4 x 10(-7) mol/L. Moreover, the studied biosensor exhibited good accuracy and high sensitivity. The proposed method was economical and efficient, making it potentially attractive for the application to real sample analysis.