Molybdenum-containing polypyrrole self-supporting hollow flexible electrode for hydrogen peroxide detection in living cells.

A flexible electrode based on polypyrrole-supported free-standing molybdenum oxide-molybdenum disulfide/polypyrrole nanostructure (MoO3-MoS2/PPy) was synthesized. The petal-like MoO3-MoS2 sheets grown on PPy were prepared step by step through simple electrodeposition and hydrothermal methods. The corresponding surface morphological and structural characterizations were characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results showed that the prepared petal MoO3-MoS2 hybrid nanomaterials were uniformly distributed on the PPy skeleton and exhibited a three-dimensional porous network structure. The flexible electrode was used for non-enzymatic detection of hydrogen peroxide (H2O2), and the developed MoO3-MoS2/PPy nanomaterials exhibited high electrochemical sensing performance in the range of 0.3-150 µM, with the detection limit of 0.18 µM (S/N = 3). The excellent detection properties enabled the MoO3-MoS2/PPy flexible electrode to detect H2O2 released by living cells. The resulting MoO3-MoS2/PPy flexible electrode also has the advantages of customizable shape and adjustability, which provides a potential platform for constructing clinically diagnosed in vivo portable instruments and real-time environmental monitoring.

Electrochemical endotoxin aptasensor based on a metal-organic framework labeled analytical platform.

An electrochemical aptasensor for the lipopolysaccharide (LPS) detection was constructed by using copper-based metal-organic framework (Cu-MOF) as a label and the LPS aptamer of specific single-stranded DNA as a probe. The carboxyl-functionalized polypyrrole nanowires (PPy NWs) were synthesized by electrochemical polymerization method, and the amino-terminated aptamer covalently coupling with the carboxyl group of the PPy NWs was immobilized onto the modified electrode. The aptamer can specifically combine with the target LPS molecules, and Cu-MOF was labeled by adsorption based on specific interactions of LPS carbohydrate portions with anionic groups. The fabrication processes of the aptasensor were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Differential pulse voltammetry (DPV) was used to measure electrochemical performance of the aptasensor, and the electrochemical signal can be directly measured by the electrochemical redox reaction of Cu(II)/Cu(I) existed in the Cu-MOF. The electrochemical aptasensor exhibited a high sensitivity toward LPS ranging from 1.0 pg/mL to 1.0 ng/mL with a detection limit of 0.29 pg/mL. Moreover, the developed sensor was found to have good selectivity, stability and regeneration properties, and the sensor also successfully detected LPS in real tap water samples.

Copper ion-assisted gold nanoparticle aggregates for electrochemical signal amplification of lipopolysaccharide sensing.

A signal amplification electrochemical aptasensor for ultrasensitive detection of lipopolysaccharide (LPS) was fabricated. The sensor was constructed with a probe of LPS aptamer and a copper ions-mediated gold nanoparticles aggregate (Cu/Au NA) as a signal amplification material. The Cu/Au NAs comprising copper ions (Cu2+) and L-cysteine modified AuNPs were fabricated by a self-assembly process. For functionalization of the electrode, the carboxylic group of a mercaptoacetic acid self-assembly layer was covalently coupled with the amine group of the aptamer. The aptamer with high specificity and affinity can effectively gather the dissociative LPS firstly, and the Cu/Au NAs were captured by anionic groups of the carbohydrate portions from LPS molecules based on the specific interactions. With the employment of the sandwich-type biosensor, the strategy can significantly amplify the electrochemical signal for determination of trace amount of LPS. The sensing performance of the electrochemical sensor was investigated by differential pulse voltammetry (DPV) and the stripping peak currents of Cu re-oxidized to Cu2+ was used to monitor the level of LPS. The electrochemical aptasensor exhibited excellent sensitivity toward LPS with a detection limit of 0.033 pg/mL (S/N = 3). The biosensor also exhibited a high specificity toward LPS in the presence of other common interfering substances and was easily regenerated. Furthermore, the fabricated biosensor showed a good practical application for LPS determination in human serum samples.

High rate and stable symmetric potassium ion batteries fabricated with flexible electrodes and solid-state electrolytes.

Aqueous batteries designed with K-ions have outstanding potential for future energy storage applications. When coupled with cathode and anode materials both operating with the intercalation mechanism, K-ion batteries could have kinetics and stability similar to Li-ion batteries in principle but with a much lower cost. However, the electrode materials developed so far still suffer from poor stability and limited activity, especially from the anode side. Herein, a new concept of symmetric K-ion batteries was developed by using potassium Prussian blue (KPB) as a bipolar material. The KPB particles were grown on flexible and strong wiper cloth substrates that were pre-coated with polypyrrole (PPy). The use of PPy as an interlayer not only boosted electrical conductivity but also ensured uniform growth of KPB particles. The synthesized KPB@PPy@wiper electrodes have superior flexibility and stability, and exhibited two redox pairs both with remarkable kinetics. When used as bipolar electrodes in combination with a gel solid-state electrolyte, they delivered a well-defined discharge voltage plateau at ∼0.6 V with superior rate capability and cycling stability. This work could provide new insights into the design of K-ion batteries, and give new options for developing flexible solid-state devices.

3 D Porous Nickel-Cobalt Nitrides Supported on Nickel Foam as Efficient Electrocatalysts for Overall Water Splitting.

Exploring highly efficient and durable bifunctional electrocatalysts from earth-abundant low-cost transition metals is central to obtaining clean hydrogen energy through large-scale electrolytic water splitting. Porous nickel-cobalt nitride nanosheets on macroporous Ni foam (NF) are synthesized through facile electrodeposition followed by a one-step annealing process in a NH3 atmosphere. The transformation from a metal hydroxide into a metal nitride could efficiently enhance the electrocatalytic performance for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Interestingly, the incorporation of nickel further boosts the catalytic activity of cobalt nitride. When used as bifunctional electrocatalysts, the obtained nickel-cobalt nitride electrocatalyst shows good stability and superior catalytic performance toward both HER and OER with low overpotentials of 0.29 and 0.18 V, respectively, to achieve a current density of 10 mA cm-2 . The good electrocatalytic performance was also evidenced by the fabrication of an electrolyzer for overall water splitting, which exhibits a high gas generation rate for hydrogen and oxygen with excellent stability during prolonged alkaline water electrolysis. The present work provides an efficient approach to prepare a 3 D interconnected porous nickel-cobalt nitride network with exposed inner active sites for overall water splitting.

Determination of copper ions using a phytic acid/polypyrrole nanowires modified glassy carbon electrode.

This study reports a sensitive electro-analytical method for the determination of trace amounts of Cu2+ using a phytate functionalized polypyrrole nanowires (PPy NWs) modified glass carbon electrode. The phytic acid/polypyrrole (PA/PPy) NWs were prepared by an electrostatic adsorption and ultrasonic mixing. The results showed that both PPy NWs and PA/PPy NWs modified glassy carbon electrodes have electrochemical responses toward Cu2+. However, owing to the synergistic contribution between the PPy NWs and PA, the PA/PPy NWs modified electrode exhibited higher sensitivity than that of PPy NWs modified electrode. The PA/PPy NWs composites functionalized electrodes showed a good linear relationship with Cu2+ at concentration ranges of 10-60µg·L-1, and the limit of detection (S/N=3) was 3.33µg·L-1. In addition, the electrochemical sensor was applied to assay Cu2+ in real water samples.

Synthesis of a novel electrode material containing phytic acid-polyaniline nanofibers for simultaneous determination of cadmium and lead ions.

The development of nanostructured conducting polymers based materials for electrochemical applications has attracted intense attention due to their environmental stability, unique reversible redox properties, abundant electron active sites, rapid electron transfer and tunable conductivity. Here, a phytic acid doped polyaniline nanofibers based nanocomposite was synthesized using a simple and green method, the properties of the resulting nanomaterial was characterized by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A glassy carbon electrode modified by the nanocomposite was evaluated as a new platform for the simultaneous detection of trace amounts of Cd2+ and Pb2+ using differential pulse anodic stripping voltammetry (DPASV). The synergistic contribution from PANI nanofibers and phytic acid enhances the accumulation efficiency and the charge transfer rate of metal ions during the DPASV analysis. Under the optimal conditions, good linear relationships were obtained for Cd2+ in a range of 0.05-60 µg L-1, with the detection limit (S/N = 3) of 0.02 µg L-1, and for Pb2+ in a range of 0.1-60 µg L-1, with the detection limit (S/N = 3) of 0.05 µg L-1. The new electrode was successfully applied to real water samples for simultaneous detection of Cd2+ and Pb2+ with good recovery rates. Therefore, the new electrode material may be a capable candidate for the detection of trace levels of heavy metal ions.

Functionalized gold nanoparticles/reduced graphene oxide nanocomposites for ultrasensitive electrochemical sensing of mercury ions based on thymine-mercury-thymine structure.

A sensitive, selective and reusable electrochemical biosensor for the determination of mercury ions (Hg(2+)) has been developed based on thymine (T) modified gold nanoparticles/reduced graphene oxide (AuNPs/rGO) nanocomposites. Graphene oxide (GO) was electrochemically reduced on a glassy carbon substrate. Subsequently, AuNPs were deposited onto the surface of rGO by cyclic voltammetry. For functionalization of the electrode, the carboxylic group of the thymine-1-acetic acid was covalently coupled with the amine group of the cysteamine which self-assembled onto AuNPs. The structural features of the T bases functionalized AuNPs/rGO electrode were confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy and scanning electron microscopy (SEM) spectroscopy. Each step of the modification process was characterized by cyclic voltammetry (CV) and electrochemical impedence spectroscopy (EIS). The T bases modified AuNPs/rGO electrode was applied to detect various trace metal ions by differential pulse voltammetry (DPV). The proposed biosensor was found to be highly sensitive to Hg(2+) in the range of 10 ng/L-1.0 µg/L. The biosensor afforded excellent selectivity for Hg(2+) against other heavy metal ions such as Zn(2+), Cd(2+), Pb(2+), Cu(2+), Ni(2+), and Co(2+). Furthermore, the developed sensor exhibited a high reusability through a simple washing. In addition, the prepared biosensor was successfully applied to assay Hg(2+) in real environmental samples.

Excellent anti-corrosive pretreatment layer on iron substrate based on three-dimensional porous phytic acid/silane hybrid.

A novel, highly effective and environmentally friendly film-forming material, phytic acid (PA)/silane (denoted as PAS) hybrid with a three-dimensional (3D) network structure, was prepared through a condensation reaction of PA with methyltrihydroxysilane generated from the hydrolysis of methyltriethoxysilane (MTES). Two kinds of PAS-based pretreatment layers, namely NaBrO3-free and NaBrO3-doped PAS layers, were fabricated on iron substrates using the dip-coating method. SEM and AFM observations showed that the as-fabricated PAS-based layers possessed a 3D porous microstructure at the nanoscale and a rough surface morphology. X-ray photoelectron spectroscopic (XPS) and attenuated total reflection infrared (ATR-IR) spectroscopic characterization demonstrated that the above PAS layers bound to the iron surface via the -P-O- bond. Moreover, analyses of steady-state polarization curves and electrochemical impedance spectroscopic (EIS) data indicated that the corrosion rates of the iron substrates decreased considerably in the presence of the two PAS-based pretreatment layers. In particular, the NaBrO3-dosed PAS layer displayed the better corrosion resistance ability as well as maintaining the original microstructure and surface morphology. The PAS-based pretreatment layers are expected to act as substitutes for chromate and phosphate conversion layers and will find widespread application in the surface pretreatment of iron and steel materials due to the advantages of being environmentally friendly, the rapid film-forming process, and, especially, the nanoporous microstructure and rough surface morphology.

Aqueous-organic phase-transfer of highly stable gold, silver, and platinum nanoparticles and new route for fabrication of gold nanofilms at the oil/water interface and on solid supports.

A simple but effective aqueous-organic phase-transfer method for gold, silver, and platinum nanoparticles was developed on the basis of the decrease of the PVP's solubility in water with the temperature increase. The present method is superior in the transfer efficiency of highly stable nanoparticles to the common phase-transfer methods. The gold, silver, and platinum nanoparticles transferred to the 1-butanol phase dispersed well, especially silver and platinum particles almost kept the previous particle size. Electrochemical synthesis of gold nanoparticles in an oil-water system was achieved by controlling the reaction temperature at 80 degrees C, which provides great conveniences for collecting metal particles at the oil/water interface and especially for fabricating dense metal nanoparticle films. A technique to fabricate gold nanofilms on solid supports was also established. The shapes and sizes of gold nanoparticles as the building blocks may be controllable through changing reaction conditions.

Electrochemical synthesis of gold nanocrystals and their 1D and 2D organization.

Size-controlled gold nanocrystals were conveniently synthesized through direct electroreduction of bulk AuCl(4)(-) ions in the presence of poly(N-vinylpyrrolidone) (PVP). PVP greatly enhanced the gold particle formation process and also significantly retarded the gold electrodeposition process, allowing the electrochemical synthesis of gold nanocrystals to be carried out in the form of simple electroreduction. This novel electrochemical method may be extended to synthesis of other noble metal nanoparticles with controllable size on a large scale. The PVPK90-protected gold nanocrystals spontaneously self-assembled into nearly ordered 2D close-packed arrays and interesting 1D nanostructures. The aggregation of unstable PVPK17-protected gold nanocrystals resulted in the formation of ultrathin single-crystalline films. PVP plays multifunctional roles in controlling the size and shape of gold nanocrystals and in inducing individual gold nanocrystals to construct 1D nanostructures. The nanoparticle self-assembling technique based on PVP offers a simple, but effective, path to organize individual gold nanoparticles into various 1D and 2D nanostructured materials.