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Capillary isoelectric focusing (CIEF) was first performed in an open tubular mode. It depended on an immobilized pH gradients from the polymerization of several solutions, which contained acrylamide, N,N'-methylenebisacrylamide, allylamine, and acrylic acid. Different ratios of the basic and acidic monomers lead to solutions of various pHs. When injected into a capillary in the sequence of their pHs, the solutions polymerized and resulted into polymers with a series of isoelectric points (pIs). These polymers formed a covalently attached hydrophilic layer in the capillary, acting as both column bonding and carrier ampholytes. When five polymers were orderly lined up in a capillary, an immobilized pH gradient was established. This open tubular column was subjected to CIEF, showing excellent performance properties for protein focusing. 10.1021/ac902223y

A noninvasive fiber material-based wearable electrochemical sensor to continuously monitor the glucose level in sweat is highly desirable for smart fabrics for personal diabetes management. To achieve it, the key challenge is to construct fibers with high stretchability and excellent electrochemical performance. Herein, a highly stretchable Ni-Co metal-organic framework/Ag/reduced graphene oxide/polyurethane (Ni-Co MOF/Ag/rGO/PU) fiber-based wearable electrochemical sensor is fabricated for monitoring the glucose level in sweat continuously with high sensitivity and accuracy. The rGO/PU fiber was simply produced by an improved wet spinning technology, and the Ni-Co MOF nanosheet was coated on its surface to prepare the Ni-Co MOF/Ag/rGO/PU (NCGP) fiber electrode. The Ni-Co MOF has a large specific surface area and high catalytic activity, which enables the fiber sensors with good electrochemical performance with a high sensitivity of 425.9 μA·mM -1 ·cm -2 and a wide linear range of 10 μM-0.66 mM. More importantly, the NCGP fiber electrode also shows extremely high stretching and bending stability under mechanical deformation. Also, the NCGP fiber electrode has high selectivity and long-time storage stability. Moreover, the NCGP fiber-based three-electrode system was sewn with an absorbent fabric and fixed on a stretchable polydimethylsiloxane film substrate to form a nonenzymatic sweat glucose wearable sensor, which realized real-time monitoring of glucose in human sweat with high accuracy. This indicates that our designed NCGP fiber can be used as a wearable electrochemical sensor for the bio-diagnostics of body sweat.

Two-dimensional (2D) ultrathin nickel-cobalt phosphate nanosheets were synthesized using a simple one-step hydrothermal method. The morphology and structure of nanomaterials synthesized under different Ni/Co ratios were investigated by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Moreover, the influence of nanomaterials' structure on the electrochemical performance for glucose oxidation was investigated. It is found that the thinnest nickel-cobalt phosphate nanosheets synthesized with a Ni/Co ratio of 2:5 showed the best electrocatalytic activity for glucose oxidation. Also, the ultrathin nickel-cobalt phosphate nanosheet was used as an electrode material to construct a nonenzymatic electrochemical glucose sensor. The sensor showed a wide linear range (2-4470 μM) and a low detection limit (0.4 μM) with a high sensitivity of 302.99 μA·mM -1 ·cm -2 . Furthermore, the application of the as-prepared sensor in detection of glucose in human serum was successfully demonstrated. These superior performances prove that ultrathin 2D nickel-cobalt phosphate nanosheets are promising materials in the field of electrochemical sensing.

Ni-MOF (metal-organic framework)/Ni/NiO/carbon frame nanocomposite was formed by combing Ni and NiO nanoparticles and a C frame with Ni-MOF using an efficient one-step calcination method. The morphology and structure of Ni-MOF/Ni/NiO/C nanocomposite were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and energy disperse spectroscopy (EDS) mapping. Ni-MOF/Ni/NiO/C nanocomposites were immobilized onto glassy carbon electrodes (GCEs) with Nafion film to construct high-performance nonenzymatic glucose and H 2 O 2 electrochemical sensors. Cyclic voltammetric (CV) study showed Ni-MOF/Ni/NiO/C nanocomposite displayed better electrocatalytic activity toward glucose oxidation as compared to Ni-MOF. Amperometric study indicated the glucose sensor displayed high performance, offering a low detection limit (0.8 μM), a high sensitivity of 367.45 mA M -1 cm -2 , and a wide linear range (from 4 to 5664 μM). Importantly, good reproducibility, long-time stability, and excellent selectivity were obtained within the as-fabricated glucose sensor. Furthermore, the constructed high-performance sensor was utilized to monitor the glucose levels in human serum, and satisfactory results were obtained. It demonstrated the Ni-MOF/Ni/NiO/C nanocomposite can be used as a good electrochemical sensing material in practical biological applications.

This paper describes the immobilization of gold nanoparticles on metal-metalloporphyrin frameworks (AuNPs/MMPF-6(Fe)) through electrostatic adsorption. The composites were characterized by powder X-ray diffraction, zeta potential, transmission electron microscopy, electrochemical impedance spectroscopy, and voltammetric methods. MMPF-6(Fe) exhibited a pair of redox peaks of the Fe(III)TCPP/Fe(II)TCPP redox couple. The AuNPs/MMPF-6(Fe)-based electrochemical sensor demonstrates a distinctly higher electrocatalytic response to the oxidation of hydroxylamine due to the synergic effect of the gold metal nanoparticles and metal-metalloporphyrin matrix. The voltammetric current response exhibits two linear dynamic ranges, 0.01-1.0 and 1.0-20.0 μmol L(-1), and the detection limit was as low as 0.004 μmol L(-1) (S/N = 3). Moreover, the biosensor exhibits high reproducibility and stability in acid solution. Our work not only offers a simple way to achieve the direct electrochemical behavior of metalloporphyrin but also expands the potential applications of MOFs-based composites in bioanalysis.

In the present work, a novel label-free chemiluminescent (CL) immunoassay method was designed by employing smart CuS nanoparticles (CuSNPs) as peroxidase mimetics. The CuSNPs were synthesized through a simple coprecipitation method, and showed high catalytic activity and stability. This efficient label-free CL immunoassay could be easily achieved through a simple strategy. First, CuSNPs dispersed in chitosan were modified on the epoxy-functionalized glass slide to form a solid CL signal interface. Streptavidin was then used to functionalize CuSNPs to capture the biotinylated antibody, further producing a sensing interface. After online incubation with antigen molecules, the formed antibody-antigen complex on the biosensing substrate could prevent the diffusion channel of CL substrate toward the signal interface, and restrained the mimic enzyme-catalyzed CL reaction, finally resulting in the decrease of CL signals of the assay system. Compared to the label-based CL immunoassay, the proposed label-free assay mode is more simple, cheap and fast. Using a model analyte alpha-fetoprotein, the label-free CL immunoassay method had a linear range of 0.1-60 ng/mL and a low detection limit of 0.07 ng/mL. Moreover, the peroxidase mimetic-based label-free CL immunoassay system showed good specificity, acceptable repeatability, and good accuracy. The study provided a promising strategy for the development of highly efficient label-free CL immunoassay system.

A simple cyclic voltammetric method was applied to assemble and orient a model protein, namely, myoglobin (Mb), into a biocompatible Brij 56 film. Ultraviolet-visible and circular dichroism spectra indicated that Mb in Brij 56 matrix preserved its secondary structure. Fourier transform infrared spectra confirmed the formation of hydrogen bonds between Mb and Brij 56. These hydrogen bonds acted as the electron tunnel to transfer electrons from Mb's active sites to the underlying glassy carbon electrode. Effective direct electron transfer of Mb was realized with the presence of a couple of quasi-reversible and well-defined redox peaks at -310 mV (vs standard calomel electrode) in the studied potential range. The peaks were attributed to the redox couple of heme Fe(II)/Fe(III) of the well-oriented Mb in Brij 56 matrix. The surface coverage and the electron transfer rate (ks) of Mb immobilized into the Brij 56 film was ∼4.9×10(-11) mol cm(-2) and 72.6±3.0 s(-1), respectively. An excellent electrocatalytic response of the immobilized Mb toward nitrite in the absence of electron transfer mediators was observed. These results emphasized that the biomimetic Brij 56 could be used as an attractive material for immobilizing proteins and constructing biosensors.

Graphene oxide (GO) nanosheets were immobilized onto the capillary wall using 3-aminopropyldiethoxymethyl silane as coupling agent. Graphene coated column (G@column) was fabricated by hydrazine reduction of GO modified column. Scanning electron microscopy (SEM) images provided visible evidence of the GO grafted on the capillary wall. Energy dispersive X-ray spectrometry (EDS) indicated the high coverage of the GO on the capillary wall. The G@column exhibited a pH-dependent electroosmotic flow (EOF) from anode to cathode in the pH range of 3-9 while the graphene oxide coated column (GO@column) showed a constant EOF. Both GO@column and G@column were evaluated for open-tubular capillary electrochromatography (OT-CEC). The GO@column was also evaluated for open-tubular capillary liquid chromatography (OT-CLC). Good separation of the tested neutral analytes on the GO@column was achieved on the basis of a typical reversed-phase behavior. On the contrary, G@column showed poor separation performance because of the strong π-π stacking and hydrophobic interactions between graphene and polyaromatic hydrocarbons. The high coverage of GO improved the column phase ratio which makes the GO@column promising for OT-CLC separation. Five of the major known proteins including three glycoisoforms of ovalbumin in chicken egg white were identified in a single run on the GO@column with phosphate buffer (5 mM, pH 7.0) and an applied voltage of 20 kV. The run-to-run, day-to-day, and column-to-column reproducibilities are evaluated by calculating the relative standard deviations (RSDs) of the EOF in OT-CEC and retention time of naphthalene in OT-CLC, respectively. These RSD values were found to be less than 3%.

A dramatic visible light photoelectrochemical sensing platform for the detection of pesticide molecules at zero potential (versus saturated calomel electrode) was first constructed using poly(3-hexylthiophene)-functionalized TiO(2) nanoparticles. Poly(3-hexylthiophene) (P3HT) was synthesized via chemical oxidative polymerization with anhydrous FeCl(3) as the oxidant, 3-hexylthiophene as the monomer, and chloroform as the solvent, and the functional TiO(2) nanoparticles were facilely prepared by blending TiO(2) nanoparticles and P3HT in chloroform solution. The resulting photoelectrocatalysts were characterized by scanning electron microscopy, Raman spectroscopy, and X-ray diffractometry. Under visible light irradiation, P3HT generated the transition from the valence band to the conduction band, delivering the excited electrons into the conduction band of TiO(2) and then to the glassy carbon electrode. Simultaneously, a positive charged hole (h(+)) of TiO(2) may form and migrate to the valence band of P3HT, which can react with H(2)O to generate (•)OH, and then it converted chlopyrifos into chlopyrifos(•) that promoted the amplifying photocurrent response. On the basis of the proposed photoelectrochemical mechanism, a methodology for sensitive photoelectrochemical sensing for chlopyrifos at zero potential was thus developed. Under optimal conditions, the proposed photoelectrochemical method could detect chlopyrifos ranging from 0.2 to 16 μmol L(-1) with a detection limit of 0.01 μmol L(-1) at a signal-to-noise ratio of 3. The photoelectrochemical sensor had an excellent specificity against the other pesticides and could be successfully applied to the detection of reduced chlopyrifos in green vegetables, showing a promising application in photoelectrochemical sensing.

A novel photoelectrochemical sensor for detection of the organophosphorus pesticide (OP) dichlofenthion using nanometer-sized titania coupled with a screen-printed electrode is presented. Nonelectroactive dichlofenthion can be indirectly determined through the photocatalytical degradation of dichlofenthion with nanometer-sized titania. The electrochemical characterization and anodic stripping voltammetric performance of dichlofenthion were evaluated using cyclic voltammetric (CV) and differential pulse anode stripping voltammetric (DPASV) analysis, respectively. DPASV analysis was used to monitor the amount of dichlofenthion and provide a simple, fast, and facile quantitative method for dichlofenthion. Operational parameters, including the photocatalysis time, pH of buffer solution, deposition potential, and accumulation time have been optimized. The stripping voltammetric response is linear over the 0.02-0.1 and 0.2-1.0 μmol/L ranges with a detection limit of 2.0 nmol/L. The assay result of dichlofenthion in green vegetable with the proposed method was in acceptable agreement with that of the gas chromatograph-mass spectrometer (GC-MS) method. The promising sensor opens a new opportunity for fast, portable, and sensitive analysis of OPs in environmental samples.