Copper-cobalt dual-site on N-doped carbon nanotube with dual-promoted synergy for glucose electrochemical detection.

Doping specific active sites and accelerating the decisive step of glucose catalysis to construct highly active glucose sensing electrochemical catalysts remains a major challenge for glucose sensing. Herein, we report the detailed design of Cu-Co dual active site N-doped carbon nanotube (CuCo-NCNTs) obtained by electrodeposition modification, programmed warming and calcination for electrochemical glucose detection. In the CuCo-NCNTs material system, Cu serves as the main active site for glucose sensing. Co with good adsorption of hydroxyl groups acts as the site providing hydroxyl groups to provide oxygen source for Cu oxidized glucose sensing. The synergistic effect between the two active sites in the Cu-Co system and the abundant micro-reactive sites exposed by carbon nanotubes greatly ensure the excellent electrocatalytic performance of glucose oxidation reaction. Therefore, CuCo-NCNTs have good electrocatalytic performance with a sensitivity of 0.84 mA mM-1 cm-2 and a detection limit of 1 µM, and also have excellent stability and specificity. DFT calculations elucidate the decisive steps of H-atom removal in the oxidation of glucose by Cu active site N-doped carbon nanotube (Cu-NCNTs) and Co active site N-doped carbon nanotube (CuCo-NCNTs) materials, illustrating the role of oxygen source provided by hydroxyl group adsorption in the electrochemical sensing process of glucose, thus demonstrating that the electrochemical sensing signal of glucose can be effectively enhanced when cobalt species that readily adsorb hydroxyl groups are introduced into the materials.

Alkaline liquid-derived NaxTi11.5MoVOx/C-40 material with controlled electron transfer rate for sensitive electrochemical detection of dopamine.

The neurotransmitter dopamine (DA) is associated with many physiological and pathological processes, so the importance of low detection limits and high sensitivity analysis cannot be overstated, especially for early disease detection. Here, 2 M NaOH aqueous solution is used to precipitate metal ions in an ethanol solution containing carbon black (CB), and then nanocomposite catalysts (NaxTi11.5MoVOx/C-40 (40 denoted as 40 mg CB)) were obtained by calcining the precipitation. When used for DA detection, NaxVOx acts as the main active site for electrochemical oxidation of DA and NaxTi11.5MoOx plays a role in facilitating the binding of DA to the active site and stabilizing the active site. The NaxTi11.5MoVOx/C-40 electrochemical biosensor has a limit of detection (LOD) of 0.003 µM with a linear range of 0.005-51.665 µM for DA. This sensor can be used to sensitively identify the concentration of DA in human blood and urine. Catalysts containing varying amounts of CB exhibit diverse electron transfer rates, and surprisingly, we found that the appropriate electron transfer rate is optimal for the detection of low concentrations of DA. Because the performance of the electrochemical biosensors is affected by both the activity of the catalysts and the accuracy of the electrochemical testing instrumentation. To better explain this phenomenon, we propose the concept of resolution (Rn) and present the formula to derive it, offering a new approach to evaluating the performance of electrochemical biosensors.

Enhanced electrochemical glucose sensing of Co/Cu-MOF by hydroxyl adsorption induced reactive oxygen species.

Exploring the factors affecting the electrochemical catalytic signal of an organic-metal material sensor and analyzing the decisive steps of the glucose oxidation behavior are challenging problems. Here, we designed a copper-cobalt-based organic backbone with excellent sensing properties based on the nanostructure of "ultramicroelectrodes", and explored the role of different hydroxyl adsorption capacities in the sensing process of glucose oxidation. Dimethylimidazole was used as a starting substrate, and then copper and cobalt ions were introduced by hydrothermal treatment to prepare a copper-cobalt-based organic backbone (Co/Cu-MOF) with good electrochemical glucose sensing ability. Due to the abundant micro-reaction sites of Co/Cu-MOF and the ability to control the hydroxyl group adsorption by adjusting the Co/Cu ratio, excellent electrocatalytic sensing performance was ensured. Co/Cu-MOF (Co/Cu molar ratio of 20 : 1) showed the best adsorption capacity for hydroxyl groups with a sensitivity of 0.45 mA mM-1 cm-2 and a LOD of 0.82 µM in electrochemical glucose sensing. In summary, the sensing performance was effectively improved by adding adsorbed hydroxyl groups to provide an oxygen source for the glucose oxidation step without changing the specific components.

Fabrication and simulation of a layered ultrahigh thermal conductive material made of self-assembled graphene and polydopamine on a copper substrate.

A composite material of graphene (G) and polydopamine (PDA) on a copper (Cu) substrate (G/PDA@Cu) was fabricated successfully by sequential immersion deposition in a dopamine solution and an aqueous graphene oxide suspension before annealing. Optimum preparation conditions were explored by the orthogonal experimental method. The morphology and chemical composition of G/PDA@Cu were studied systematically by a series of characterization techniques. The thermal-conductive performance was evaluated by a laser flash thermal analyser. The thermal conductivity of G/PDA@Cu was 519.43 W m-1 K-1, which is ultrahigh and 30.50% higher than that of the Cu substrate. The adhesion force between G/PDA and the Cu substrate was 4.18 mN, which means that G bonds to the Cu substrate tightly. The model simulation also showed that G/PDA@Cu exhibits excellent thermal conductivity, allowing it to play a significant role in the thermal management of advanced electronic chips. The thermal-conductive devices using this material were prepared for practical applications.

Effect of Thermal Annealing on Conformation of MEH-PPV Chains in Polymer Matrix: Coexistence of H- and J-Aggregates.

In diluted solid solution using poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and polymethyl methacrylate (PMMA) or polystyrene (PS), both aggregated and extended conformations could be formed according to the weight ratio. Aggregated conformation in as-cast MEH-PPV/PMMA film presented a J-aggregate-like photoluminescence (PL) emission. After annealing at 160 °C, its PL showed characteristics of both J- and H-aggregates at the same time; however, extended conformation showed an oligomer-like emission, which was not sensitive to either measurement temperature or annealing temperature. Thus, the conformation transition between aggregated and extended is unlikely to happen in MEH-PPV/PMMA blends during thermal annealing. On the contrary, in MEH-PPV/PS blends, extended conformation dominated in as-cast film with oligomer-like emissions; after annealing at 160 °C, both J- and H- aggregate-like PL emissions were observed, indicating the conformation transitioned from extended to aggregated. Therefore, our work may suggest a new method to manipulate photophysical properties of conjugated polymers by combining appropriate host matrix and thermal annealing processes.

Spectrophotometric determination of the activity of alkaline phosphatase and detection of its inhibitors by exploiting the pyrophosphate-accelerated oxidase-like activity of nanoceria.

The oxidase-like activity of nanoceria is low. This limits its practical applications. It is demonstrated here that pyrophosphate ion (PPi) can improve the oxidase-like activity of nanoceria. Specifically, nanoceria catalyzes the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to give a blue product (oxTMB) with an absorption peak at 645 nm in the presence of PPi. If, however, alkaline phosphatase (ALP) is present, it will hydrolyze PPi, and this results in a decreased oxidase-like activity of nanoceria. Hence, less blue oxTMB willl be formed. On the other hand, if the ALP inhibitor Na3VO4 is added to the system, the oxidase-like activity of nanoceria is gradually restored. On the basis of the above results, a spectrophotometric method was developed for determination of the activity of ALP. It works in the 0.5 to 10 mU.mL-1 activity range and has a 0.32 mU.mL-1 detection limit. Na3VO4 causes a 50% ALP inhibition if present in 71 µM concentration. The assay was successfully applied to the determination of ALP in spiked human serum and gave good recoveries. Graphical abstract Schematic presentation of pyrophosphate (PPi)-induced acceleration of the oxidase-like activity of nanoceria (CeO2) for determination of alkaline phosphatase enzyme (ALP) activity and its inhibitor NaVO3.

Reduced graphene oxide nanosheets modified with plasmonic gold-based hybrid nanostructures and with magnetite (Fe3O4) nanoparticles for cyclic voltammetric determination of arsenic(III).

The authors have fabricated reduced graphene oxide nanosheets (rGO) supported with Fe3O4 nanoparticles and Ag/Au hollow nanoshells. The material was placed on a glassy carbon electrode which is shown to enable highly sensitive determination of As(III) which is first preconcentrated from solution at a potential of -0.35 V (versus Ag/AgCl) for 100 s. The electrode, typically operated at a working potential as low as 0.06 V, has a linear response in the 0.1 to 20 ppb As(III) concentration range and a 0.01 ppb detection limit. The electrochemical sensitivity is 52 µA ppb-1. The high sensitivity is assumed to be the result of various synergistic effects. The method was applied to ultratrace (0.1 ppt) determination of As(III) in real water samples. Graphical abstract The hybrid displays a wide linear response in the 0.1 to 20 ppb As(III) concentration range and a 0.01 ppb detection limit. The high sensitivity is attributed to various synergistic effects. The method was applied to ultratrace determination of As(III) in real water samples.

Highly sensitive fluorescent detection of glutathione and histidine based on the Cu(ii)-thiamine system.

In this work, we propose a fluorescence method for the simultaneous detection of glutathione (GSH) and histidine (His) based on the Cu(ii)-thiamine (Cu(ii)-TH) system. It is well established that non-fluorescent thiamine (TH) can be oxidized by Cu(ii) to generate fluorescent thiochrome (TC) under alkaline conditions. The introduction of GSH and His can inhibit the oxidation of TH by Cu(ii) due to the strong affinity between Cu(ii) and GSH or His. With this strategy, the detection limit for GSH and His is 10.5 nM and 26.4 nM, respectively. The developed method shows several obvious advantages: (1) simplicity in design and operation without the utilization of fluorescent nanomaterials or probes; (2) time-saving detection process since all the detection process is completed within 15 min; (3) cost-effectiveness by using TH as the fluorescent substrate; and (4) higher sensitivity and good selectivity. Therefore, it shows great potential in biosensing fields.

Fluorescence assay for alkaline phosphatase based on ATP hydrolysis-triggered dissociation of cerium coordination polymer nanoparticles.

Alkaline phosphatase (ALP) is a significant biomarker for diagnostics. Simple, selective and sensitive detection of ALP activity is thus of critical importance. In this study, an artful fluorescence assay for ALP is proposed based on adenosine triphosphate (ATP) hydrolysis-triggered disassociation and fluorescence quenching of cerium coordination polymer nanoparticles (CPNs). ATP, a recognized natural substrate of phosphatase, can serve as a superb "antenna" to sensitize the luminescence of Ce3+ with the aid of tris(hydroxymethyl) aminomethane (Tris), forming Ce3+-ATP-Tris CPNs. In the presence of ALP, ATP will be catalytically converted into adenosine and inorganic orthophosphate, however neither of them can sensitize Ce3+ in alkaline media. As a result, the obtained CPNs are disassociated, inducing the quenching of the fluorescence. On this basis, a straightforward fluorescence assay for ALP activity is rationally developed. The fluorescence quenching efficiency shows a linear relationship for ALP within the activity range from 0.1 to 10 mU mL-1 with a detection limit of 0.09 mU mL-1 under the optimal experimental conditions. Moreover, this facile yet effective fluorescence method featured simplicity, cost-effectiveness, high sensitivity and high selectivity and can be successfully utilized for the quantitative detection of ALP in human serum samples.

Fluorometric determination of sulfide ions via its inhibitory effect on the oxidation of thiamine by Cu(II) ions.

A fluorometric assay is described for sulfide ions determination. It is based on the finding that the oxidation of the non-fluorescent substrate thiamine (TH) by Cu(II) in basic solution to form fluorescent thiochrome is inhibited by sulfide ions. This results in a decrease in fluorescence intensity which is proportional to the concentration of sulfide ions. Under the optimized conditions, the decrease in fluorescence, best measured at excitation/emission wavelengths of 370/440 nm, decreases linearly in the 0.03 to 2.5 µM sulfide ions concentration range. The detection limit is 20 nM. The method shows excellent selectivity over many potentially interfering ions and has been successfully applied to the determination of sulfide ions in spiked tap water, lake water and the synthetic wastewater samples. The method is time-saving and environmentally friendly, and in our perception shows a great potential in water quality inspection and environmental monitoring. Graphical abstract A fluorescent assay for sulfide ions detection is proposed based on its inhibitory effect on the oxidation of thiamine by Cu(II) ions.

Free-Standing Monolayered Metallic Nanoparticle Networks as Building Blocks for Plasmonic Nanoelectronic Junctions.

The effective coupling of optical surface plasmons (SPs) and electron transport in a plasmonic-electronic device is one of the fundamental issues in nanoelectronics and the emerging field of plasmonics, and offer promise in providing a solution to next generation nanocircuits in which all coupling is in the near field. Attempts toward this end, however, are limited because of the integration challenge to compatible nanodevices. To date, direct electrical detection of SP-electron coupling from metallic nanostructures alone are not reported, and thus it remains a great experimental challenge. In this paper, we succeed in preparing a new suspended-film-type nanoelectronic junction, in which free-standing 2D fractal nanoparticle networks act as plasmonically active nanocomponents. Direct electrical detection of optical collective SPs was evidenced by photocurrent response of the junction upon illumination. Room-temperature I-V characteristics, differing from nonlinear to Ohmic behaviors, are found to be sensitive to the nanometer-scale morphology changes of the nanomembranes. The finding and approach may enable the development of advanced plasmonic nanocircuits and new nanoelectronics, nanophotonics, and (solar) energy applications.

Bacteriorhodopsin/Ag nanoparticle-based hybrid nano-bio electrocatalyst for efficient and robust H2 evolution from water.

Searching for novel hybrid electrocatalysts with high activity and strong durability for a direct electrochemical hydrogen evolution reaction (HER) is extremely desirable but still remains a significant challenge. Herein, we report a novel solid carbon cloth-supported hybrid nano-bio electrocatalyst, decorated with Ag nanoparticles and proton-pumping bacteriorhodopsin (bR) (Ag/bR/CP) that were prepared by in situ electroless deposition and vesicle fusion technology, respectively. When applied as a hydrogen evolution cathode, the Ag/bR/CP shows a low onset overpotential of 63 mV, good durability (no detectable change in its catalytic activity for up to 1000 cycles in alkaline media), and enhanced HER performance under 550 nm irradiation, attributed to the activation of Ag and synergistic effects following light absorption, demonstrated by photoelectrochemical measurements.

Fine-tuning the LSPR response of gold nanorod-polyaniline core-shell nanoparticles with high photothermal efficiency for cancer cell ablation.

Gold nanorods (GNRs) with suitable aspect ratios have strong localized surface plasmon resonance (LSPR) absorption and scattering in the 650-900 nm near-infrared region, which make them attractive for in vitro or in vivo imaging and photothermal cancer therapy. However, they often suffer from cytotoxicity and instability for practical applications, and therefore need further surface modification to solve these issues. In this study, GNRs coated with biocompatible polyaniline (PANI) were used as a stable and highly efficient photothermal agent for cancer cell ablation. Fine-tuning the LSPR response of the GNR-PANI core-shell nanoparticles via thickness-controlled coating of the PANI nanoshells, optimizes the photothermal conversion efficiency of the agent. As a result of the contributions from the GNR core and PANI shell, the capability of photothermal transduction of the resultant nanoparticles at 808 nm is greatly enhanced. After exposure to a continuous NIR laser at 808 nm for ∼5 min, cancer cells were efficiently ablated requiring only a very low laser flux of 0.6 W cm-2, the lowest value reported to date for plasmonic nanostructures, showing the great potential for photothermal cancer therapy.

Synthesis of a hierarchical three-component nanocomposite structure system with enhanced electrocatalytic and photoelectrical properties.

Effective control over the morphology and size of Pd/Pt nanoparticles is currently of immense interest because their electronic, optical, and catalytic properties are superior to pure platinum nanoparticles. However, control over the nanoparticle shape is still challenging. Therefore, a novel design and synthetic route needs to be developed to obtain a high-performance catalyst. Herein, a hierarchical three-component nanocomposite structure system (HTNSS) composed of graphene, TiO(2), and Pd@Pt core-shell nanoparticles was designed and synthesized by a sequential strategy that focuses on constructing the monolithic structure rather than limited single-component counterparts. The resulting composites were characterized by various techniques, which showed that the Pd@Pt core-shell nanoparticles were preferentially deposited on the peripheral interface of the graphene and TiO(2) nanoparticles. The photoelectrical and catalytic performances were obviously improved relative to the commercially available E-TEK Pt/C owing to their synergistic effect.

Anatase TiO2 nanocrystals with exposed {001} facets on graphene sheets via molecular grafting for enhanced photocatalytic activity.

Owing to their extensive practical applications and fundamental importance, the controllable synthesis of well-faceted anatase TiO(2) crystal with high percentage of reactive facets has attracted increasing attention. Here, nano-sized anatase TiO(2) sheets mainly dominated by {001} facets had been prepared on graphene sheets by using a facile solvothermal synthetic route. The percentage of {001} facets in TiO(2) nanosheets was calculated to be ca. 64%. The morphologies, structural properties, growth procedures and photocatalytic activities of the resultant TiO(2)/graphene nanocomposites were investigated. In comparison with commercial P25 and pure TiO(2) nanosheets, the composite exhibited significant improvement in photocatalytic degradation of the azo dye Rhodamine B under visible light irradiation. The enhancement of photocatalytic activity and stability was attributed to the effective charge anti-recombination of graphene and the high catalytic activity of {001} facets.

A novel detection technique of hydrazine hydrate: modality change of hydrogen bonding-induced rapid and ultrasensitive colorimetric assay.

Ultrasensitive visual detection of hydrazine hydrate using a Au nanoparticles-based colorimetric sensing system (ANCSS) is reported for the first time, which is based on the hydrogen bonding recognition and the modality change of hydrogen bonding from "linear" (simple hydrogen bond interactions) to "nonlinear" (a complicated hydrogen bond network) between as-modified Au nanoparticles (Au NPs).

Adsorption and desorption of antimony acetate on sodium montmorillonite.

The adsorption of antimony acetate (Sb(OAc)(3)) on sodium montmorillonite (Na-MMT) was studied at five different initial concentrations, and data from the adsorption isotherm were modeled using the Langmuir, Freundlich and D-R isotherm equations. The kinetics of adsorption was also discussed using three kinetic models: the pseudo-first-order, the pseudo-second-order and the intraparticle diffusion model. The rate constants of pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetics, and the amount of Sb(OAc)(3) adsorbed at equilibrium were determined. Moreover, the desorption of Sb(OAc)(3) from several kinds of Sb-MMT (Na-MMT was intercalated by antimony acetate) was investigated at room temperature and 180 °C. The results show that according to the maximum amounts of adsorbate and correlation coefficients calculated from the three isotherm equations mentioned above, the corresponding data from adsorption experiments fit fairly well to the Langmuir isotherm. The adsorption data show a good compliance with the pseudo-second-order kinetic model and also follow the intraparticle diffusion model up to 30 min. The equilibrium adsorption capacity of Sb(OAc)(3) on MMT is close to the cation exchange capacity (CEC) of the montmorillonite. The desorption amount of Sb(OAc)(3) is correlated with both the temperature of desorption and the drying temperature of Sb-MMT.