A disposable sensor based on immobilization of acetylcholinesterase to multiwall carbon nanotube modified screen-printed electrode for determination of carbaryl

A simple method has been devised for immobilization of acetylcholinesterase (AChE) covalent bonding to a multiwall carbon nanotube (MWNT)-cross-linked cellulose acetate composite on a screen-printed carbon electrode (SPCE) and a sensitive and disposable amperometric sensor for rapid determination of carbaryl pesticide is proposed. The immobilized enzyme was preserved on this film because of the excellent biocompatibility and non-toxicity of cellulose acetate. Based on the inherent conductive properties of the MWNT, the immobilized AChE had greater affinity for ATCl and excellent catalytic effect in the hydrolysis of ATCl. MWNT improved the interface enzymatic hydrolysis reaction and increased the amperometric response of the sensor. Under optimum conditions, the inhibition of carbaryl on AChE increased linearly with the increasing concentration of carbaryl in two ranges, from 0.01 to 0.5 μg mL⁻¹ and from 2 to 20 μg mL⁻¹, with the correlation coefficients of 0.9985 and 0.9977, respectively. The detection limit was 0.004 μg mL⁻¹ taken as the concentration equivalent to 10% decrease in signal. The sensor showed acceptable stability, accuracy and could be fabricated in batches, thus it is economic and portable. This type of disposable enzyme-based amperometric sensor has extensive application potential in environmental monitoring of pesticides.     

Influence of pencil lead hardness on voltammetric response of graphite reinforcement carbon electrodes

This work studied the voltammetric response of graphite reinforcement electrodes made of different pencil lead hardness. The studies showed that harder graphite leads, regardless of their manufacturer, are more appropriate as electrode material for voltammetric purposes due to their higher peak currents, increasing sensitivity and reproducibility, with ΔEp closer to the theoretical value for a reversible system.     

FEM model of the ohmic resistance of IP-SOFCs

In the present work, the ohmic resistance of an integrated planar-SOFC (IP-SOFC) has been evaluated by developing a model whose equations have been solved numerically through an FEM method. The model allows to estimate the distribution of voltage and current density in the cell. A comparison between simulated and experimental data of area specific resistance is reported, which shows satisfactory agreement. The mathematical model has also been used to carry out some parametric studies for optimisation purposes. Indeed, a reduction in cell pitch length and an increase in electrode thickness are predicted to lead to a reduction in ohmic losses in IP-SOFCs.     

Preparation and characterization of metal-complex imprinted PVDF hollow fiber membranes

Using nickel-2,2′-dipyridyl complex as a template, N-vinyl-2-pyrrolidone as the metal coordination functional monomer, and ethylene glycol dimethacrylate as the crosslinker, polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membrane as the supported membrane, metal complex imprinted polymeric membranes were prepared. The association constant of template-monomer interaction in the prepolymerization solution was estimated to be 4.38 × 10⁴ (L/mol)² by spectrophotometric titration analysis. The attenuated total reflection Fourier transform infrared spectroscopy and scanning electron micrograph characterization indicated that the surface of the support PVDF membrane was completely coated by the imprinted polymer layer after modification. The imprinted membranes exhibited the selective permeability for the template in certain nickel acetate solution. The molecularly imprinted membranes gave higher permeation separation factors at about pH 6, whereas increasing pressure would lower the separation ability. The effects of ion concentration, cations and counterions, ligand selectivity, pH, and trans-membrane pressure were investigated and the permeation performances of the imprinted membranes could be regarded as facilitated transport mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

pH and salt responsive poly(N,N-dimethylaminoethyl methacrylate) cylindrical brushes and their quaternized derivatives

We present the synthesis and characterization of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) cylindrical brushes, their pH responsiveness, and the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes. PDMAEMA brushes were prepared by atom transfer radical polymerization (ATRP) using the grafting-from strategy. Initiating efficiencies of the ATRP processes were determined by cleaving the side-chains and gel permeation chromatography (GPC) analysis. Due to the slow initiation and steric hindrance, the initiating efficiency is only around 50%. The PDMAEMA brushes show worm-like structures and pH responsiveness, as proven by dynamic light scattering (DLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Strong cationic polyelectrolyte PMETAI brushes were produced by quaternization of the PDMAEMA brushes. AFM and cryo-TEM images showed similar worm-like morphologies for the PMETAI brushes. The PMETAI brushes collapsed in solution with high concentration of monovalent salt, as proven by DLS and AFM results.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

A strategy for the electro-organic synthesis of new hydrocaffeic acid derivatives

Electrochemical treatment processes can significantly contribute to the protection of the environment through the minimization of waste and toxic materials in effluents. From a pharmaceutical point of view and due to the existing resemblance between the electrochemical and biological reactions, it can be assumed that the oxidation mechanisms on the electrode and in the body share similar principles. In this paper, the application of electrochemical studies in the design of an environmentally friendly method was delineated for the new hydrocaffeic acid (HCA, 3,4-dihydroxy hydrocinnamic acid) derivatives synthesis at carbon electrodes in an undivided cell. In this cell, the EC mechanism reaction was involved, comprising two steps alternatively; (1) electrochemical oxidation and (2) chemical reaction. In particular, the electro-organic reactions of HCA, an important biological molecule, were studied in a water–acetonitrile (90:10 v/v) mixture in the presence of benzenesulfinic acid (3) and p-toluenesulfinic acid (4). The research included the use of a variety of experimental techniques, such as cyclic voltammetry, controlled-potential electrolysis and product spectroscopic identification.     

NiCoFe/C cathode electrocatalysts for direct ethanol fuel cells

A direct ethanol fuel cell (DEFC), which is less prone to ethanol crossover, is reported. The cell consists of PtRu/C catalyst as the anode, Nafion^® 117 membrane, and Ni–Co–Fe (NCF) composite catalyst as the cathode. The NCF catalyst was synthesized by mixing Ni, Co, and Fe complexes into a polymer matrix (melamine-formaldehyde resins), followed by heating the mixture at 800 °C under inert atmosphere. TEM and EDX experiments suggest that the NCF catalyst has alloy structures of Ni, Co and Fe. The catalytic activity of the NCF catalyst for the oxygen reduction reaction (ORR) was compared with that of commercially available Pt/C (CAP) catalyst at different ethanol concentrations. The decrease in open circuit voltage (V_oc) of the DEFC equipped with the NCF catalysts was less than that of CAP catalyst at higher ethanol concentrations. The NCF catalyst was less prone to ethanol oxidation at cathode even when ethanol crossover occurred through the Nafion^®117 film, which prevents voltage drop at the cathode. However, the CAP catalyst did oxidize ethanol at the cathode and caused a decrease in voltage at higher ethanol concentrations.