Strain-Driven Bimetallic-Interface Orbital Hybridization for Hydrogen Evolution Reaction.

Enforcing the bimetallic-interface orbital hybridization in single-atom catalysts (SACs) plays a critical role in determining their catalytic activity. However, the electronic state coupling among interacting sites can be affected by surficial strain, but the relative physical mechanism still needs to be understood. Herein, we propose a series of bimetallic-hybridized SACs with structural strain to disclose their interfacial charge transfer and orbital interaction, in which asymmetric superexchange interaction between adjacent Fe and Ni sites can enforce their electronic state coupling by a structural deformation. As a result, the spin-resolved electronic structure, d-band center, and Gibbs free energy can be changed by external strain, leading to a higher reactive activity. Our findings provide a new insight into understanding the contribution of surface strain to enhancing their catalytic activity.

Ratiometric intracellular pH sensors based on nitrogen-doped graphene oxide quantum dots.

Intracellular pH (pHi) is very essential for the function of cells and organisms. Thus, it is of great scientific and technical significance to develop nanosensors for probing pHi. In this work, nitrogen-doped graphene oxide quantum dots (N-GOQDs) with fluorescent efficiency of 54% are prepared. The fluorescent spectrum excited at 340 nm contains two remarkable bands at 430 and 520 nm. Interestingly, when pH value increases from 3.6 to 10.5, the blue band at 430 nm slightly changes, while the green band at 520 nm significantly quenches. The change of fluorescent intensities also can be reflected by the variation of fluorescent color. The dual-emissive N-GOQDs are developed as ratiometric fluorescent probes for pHi, which can avoid the influence of several deviations, such as probe concentration, optical path length, and detector efficiency. As a proof of concept, pHi of Hela cells is monitored successfully. This work demonstrates the construction of nano-biosensors based on N-GOQDs with bright fluorescence, high-stability, and good biocompatibility.

Stainless steel sheets as the substrate of disposable electrochemical sensors for analysis of heavy metals or biomolecules.

In this paper, low-cost stainless steel sheets with excellent electric conductivity were utilized as the robust substrate for fabrication of disposable working electrodes. The stainless steel electrodes were modified with carbon cement and then coupled in paper-based analytical devices for analysis of heavy metals (cadmium and lead) in toys or indole-3-acetic acid (IAA) in plants, respectively. For stripping analysis of cadmium and lead, the dilution ratio of the carbon cement, the pH value of the buffer solution, the pre-deposition potential and time, and the bismuth concentration were optimized with the detection limits reaching 1 µg•L-1. After optimization of the dilution ratio of carbon cement, the similar devices could also be used for analysis of IAA at the concentration of less than 0.5 µM. This strategy could be successfully applied for differentiation of migratable lead in toys or in situ amounts of IAA in root tips of Arabidopsis thaliana in real time, respectively. Our results implied that the electric conductivity of the substrate could possibly be critical for the improvement of the analytical performance of the modified electrodes. This study suggested that stainless steel could become a suitable and cost-effective substrate for fabrication of disposable carbon-based electrodes used in electrochemical detection.

Dendritic core-shell rhodium@platinum-cobalt nanocrystals for ultrasensitive electrochemical immunoassay of squamous cell carcinoma antigen.

Squamous cell carcinoma antigen (SCCA) has great diagnostic values for its high specificity (90-96%) in diagnosis of squamous cell carcinoma especially cancers, where electrochemical immunoassay is powerful for its accurate and reliable detection of specific tumor biomarkers at very low levels. In this work, well-defined three-dimensional dendritic core-shell rhodium@platinum-cobalt nanocrystals (Rh@PtCo NCs) were facilely prepared via a simple one-pot solvothermal strategy. Taking advantage of dramatically enhanced catalytic activity of the Rh@PtCo NCs for catechol oxidation, a label-free electrochemical immunosensor was developed for highly sensitive assay of SCCA. Under optimal conditions, the electrochemical signals were linearly correlated with the logarithm of the SCCA concentration, showing a broad linear range from 0.0001 to 10.0 ng mL-1 and a ultralow detection limit of 0.04 pg mL-1 (S/N = 3). The resultant immunosensor was further exploited for actual analysis of serum samples with convinced results. This immunosensor has good expectation in actual samples analysis and provides a universal approach for detection of other tumor markers and disease surveillance.

Ultrathin PdFePb nanowires: One-pot aqueous synthesis and efficient electrocatalysis for polyhydric alcohol oxidation reaction.

Synthesis of high-efficiency catalysts for alcohol oxidation reaction caused great interest in direct alcohol fuel cells (DAFCs). Ultrathin PdFePb nanowires (NWs) with an average diameter of 2.3 nm were synthesized by a simple and fast one-pot aqueous synthesis, using octylphenoxypolyethoxyethanol (NP-40) as the structure-directing agent. The as-prepared PdFePb NWs displayed an increscent electrochemically active surface area (ECSA, 121.18 m2 g-1 Pd). For ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR), PdFePb NWs exhibited much higher activity and superior stability, outperforming those of homemade PdFe NWs, PdPb NWs, commercial Pd black and Pd/C (20 wt%). These results reveal dramatically high catalytic activity and durability of ultrathin PdFePb NWs in enhancing polyols electrooxidation.

Paper-based analytical devices for electrochemical study of the breathing process of red blood cells.

Herein we utilized the filter paper to physically trap red blood cells (RBC) to observe the breathing process of red blood cells based on the permeability of the filter paper. By integrating double-sided conductive carbon tape as the working electrodes, the device could be applied to monitor electrochemical responses of RBC for up to hundreds of minutes. The differential pulse voltammetry (DPV) peak currents increased under oxygen while decreased under nitrogen, indicating that RBC could take in and release oxygen. Further studies demonstrated that the RBC suspension could more effectively take in oxygen than the solution of hemoglobin and the supernatant of RBC, suggesting the natural advantage of RBC on oxygen transportation. This study implied that simple paper-based analytical devices might be effectively applied in the study of gas-participating reactions and biochemical detections.

Using nanostructured conductive carbon tape modified with bismuth as the disposable working electrode for stripping analysis in paper-based analytical devices.

Low cost disposable working electrodes are specifically desired for practical applications of electrochemical detection considering maturity of electrochemical stations and data collection protocols. In this paper double-sided conductive adhesive carbon tape with nanostructure was applied to fabricate disposable working electrodes. Being supported by indium tin oxide glass, the prepared carbon tape electrodes were coated with bismuth film for stripping analysis of heavy metal ions. By integrating the bismuth modified electrodes with paper-based analytical devices, we were able to differentiate Zn, Cd and Pb ions with the sample volume of around 15 µL. After the optimization of parameters, including modification of bismuth film and the area of the electrodes, etc., Pb ions could be measured in the linear range from 10 to 500 µg/L with the detection limit of 2 µg/L. Our experimental results revealed that the disposable modified electrodes could be used to quantify migrated lead from toys with the results agreed well with that using atomic absorption spectrometry. Although bismuth modification and stripping analysis could be influenced by the low conductivity of the carbon tape, the low cost disposable carbon tape electrodes take the advantages of large-scaled produced double-sided carbon tape, including its reproducible nanostructure and scaled-up fabrication process. In addition, the preparation of disposable electrodes avoids time-consuming pretreatment and experienced operation. This study implied that the carbon tape might be an alternative candidate for practical applications of electrochemical detection.

Quantum dot (QD)-modified carbon tape electrodes for reproducible electrochemiluminescence (ECL) emission on a paper-based platform.

Stable and sensitive electrochemiluminescence (ECL) detection relies on successful immobilization of quantum dots (QDs) on working electrodes. Herein, we report a new technique to apply double-sided carbon adhesive tape as the working electrode to improve the stability and reproducibility of QD-based ECL emission. CdS QD-modified electrodes were prepared by dropping and drying CdS QD suspension on the carbon adhesive tape supported by indium tin oxide (ITO) glass. The ECL detection was performed with the prepared electrode on a paper-based platform. We tested our system using H(2)O(2) of various concentrations and demonstrated that consistent ECL emission could be obtained. We attribute stable and reproducible ECL emission to the robust attachment of CdS QDs on the carbon adhesive tape. The proposed method could be used to quantify the concentration of dopamine from 1 µM to 10 mM based on the quenching effect of dopamine on ECL emission of CdS QD system using H(2)O(2) as the coreactant. Our approach addressed the problem in the integration of stable QD-based ECL detection with portable paper-based analytical devices. The similar design offers great potential for low-cost electrochemical and ECL analytical instruments.

Direct electrochemistry and electrocatalysis of hemoglobin on undoped nanocrystalline diamond modified glassy carbon electrode.

Direct electrochemistry of hemoglobin (Hb) was observed at glassy carbon electrode (GCE) modified with undoped nanocrystalline diamond (UND) and Hb multilayer films via layer-by-layer assembly. UV-VIS absorbance spectroscopy, electrochemical impedance spectroscopy and cyclic voltammograms were employed to characterize the film. The results showed that the UND had the effect of enhancing the electron transfer between Hb and the electrode surface. Hb in the multilayer films maintained its bioactivity and structure. It also exhibited a good catalytic activity towards the reduction of H(2)O(2). The reciprocal of catalytic current showed a linear dependence on the reciprocal of H(2)O(2) concentration ranging from 0.5 microM to 0.25 mM with a detection limit of 0.4 microM. The apparent Michaelis-Menten constant was estimated to be 0.019 mM.

Multilayer membranes via layer-by-layer deposition of organic polymer protected Prussian blue nanoparticles and glucose oxidase for glucose biosensing.

Polyelectrolyte multilayers (PEMs) are now widely used for bioanalytical applications. In this work, a bilayer of poly(diallydimethylammonium chloride) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS) is consecutively adsorbed on 3-mercapto-1-propanesulfonic acid modified Au electrode surfaces, forming stable, ultrathin multilayer films. Subsequently, Prussian blue nanoparticles protected by PDDA (denoted as P-PB) and negatively charged glucose oxidase (GOx) are consecutively adsorbed onto the PSS-terminated bilayer. The growth of each of the P-PB/GOx bilayers is followed quantitatively using UV-visible absorption spectroscopy and the electrochemical method. The P-PB nanoparticles can catalyze the electroreduction of hydrogen peroxide formed from enzymatic reaction at lower potential and inhibit the responses of interferents, such as ascorbic acid (AA) and uric acid (UA). Performance of the multilayer films can be tailored by controlling the number of bilayers. Under optimal conditions, a linear range of 0.10 to 11.0 mM and a detection limit of 10 microM were achieved. The glucose biosensor has good stability and reproducibility.