Measurement of the kinetic isotope effect for the oxidation of NADH at a poly(aniline)-modified electrode

Kinetic isotope measurements using [4,4-2H2]NADH and [4-1H, 4-2H]NADH have been used to investigate the mechanism of the electrochemical oxidation of NADH at poly(aniline)-poly(vinyl sulfonate)-modified electrodes. The experiments show a primary kinetic isotope effect for the reaction of 4.2. This is consistent with literature values for the corresponding isotope effect for the oxidation of NADH by two-electron oxidants in homogeneous solution. The result demonstrates that transfer of H from NADH to the modified electrode occurs in the rate-limiting step within the reaction complex.     

Nanopatterning and fabrication of memory devices from layer-by-layer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) ultrathin films

A write-read-erasable memory device was fabricated on layer-by-layer (LbL) ultrathin films prepared from poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) and poly(diallyldimethylammonium chloride) (PDDA). By use of current-sensing atomic force microscopy (CS-AFM), nanopatterns were formed by applying a bias voltage between a conductive tip (Pt-coated Si3N4 cantilever) in contact with the polymer film and gold substrate. The dependence of the nanopatterns on film thickness, applied bias, and writing speed was studied. Moreover, the height of the patterns was 3-5 times higher than the original thickness of the films, opening the possibility for three-dimensional nanopatterning. The ability of the patterns to be erased after nanowriting was also investigated. By comparing the I-V characteristics under ambient conditions and under N2 environment, a joule-heating activated, water meniscus-assisted anion doping mechanism for the nanopatterning process was determined. Write-read-erase memory device capability was demonstrated on the nanopatterns.     

Outer-sphere oxidation of ascorbate with os(bpy)33+ incorporated in nafion coatings on graphite electrodes

The electro-oxidation of ascorbate proceeds very slowly at graphite electrodes coated with Nafion. Incorporation of Os(bpy)₃²⁺ (bpy = 2,2′-bipyridine) in the coating produces a catalyzed oxidation of ascorbate at potentials where Os(bpy)₃²⁺ is oxidized to Os(bpy)₃³⁺. Analysis of the kinetic data demonstrates that the reaction between catalyst (Os(bpy)₃³⁺) and substrate (ascorbate) proceeds only within the outermost layer of the coating at the coating/solution interface. As the substrate concentration is increased, the limiting oxidation currents at coated rotating disk electrodes do not increase as rapidly as expected on the basis of current models of the behavior of polymer coated electrodes. Some possible reasons for this deviant behavior of cast Nafion coatings are suggested. Some implications of the results on the general utility of Nafion-coated electrodes in electro-catalytic applications are presented.     

Ascorbic Acid Oxidation at Nonmodified and Copper‐Modified Polyaniline and Poly‐ortho‐methoxyaniline Coated Electrodes

The electrochemical oxidation of ascorbate ions is comparatively studied at polyaniline (PANI) and poly‐ortho‐methoxyaniline (POMA) layers in absence and presence of electrodeposited copper species. In comparison to PANI, POMA layers allow decreasing the overpotential necessary for driving the ascorbate oxidation reaction. A nonlinear dependence of the ascorbate oxidation current on the polymer layer redox charge is found. Copper electrodeposited in PANI and POMA layers is electrocatalytically active for the investigated reaction. Two separate oxidation waves are observed in the case of Cu‐PANI whereas a single ascorbate oxidation wave and enhanced currents are found in the Cu‐POMA case.     

The oxidation of ascorbate at copolymeric sulfonated poly(aniline) coated on glassy carbon electrodes

Self-doped poly(aniline)s as electrode coatings to catalyze ascorbate oxidation are revisited in this article. Sulfonated poly(aniline) (SPAN) was deposited on glassy carbon electrodes as a copolymer of aniline and its sulfonated derivative, 2-aminobenzenesulfonic acid (2-ABSA). The resulting deposits are reproducible and show good stability and electroactivity at pH > 7, enabling studies at typical physiological pH values. Calibration curves were obtained using a rotating disc electrode at a sampling potential of 0.2 V, displaying linear dependence in the region 0–20 mM ascorbate. A kinetic model based on the Michaelis–Menten reaction mechanism, previously validated for poly(aniline) composites, was used to analyse the form of the calibration curve leading to values of the effective reaction constants K_ME and k′_ME. New calibration curves constructed for different sampling potentials were used to elucidate the rate limiting step at saturated kinetics. Rotating disc voltammetry performed at increasing pH (from pH 2 to 9) showed a dramatic decrease in the limiting current, without any evidence for a change in the reaction mechanism.     

Adsorptive Voltammetry of Polyelectrolyte Complex Between 11‐Ferrocenyltrimethylundecylammonium and Polyanions at Carbon Paste Electrode

For polyelectrolyte complex between cationic surfactant and polyanion, the adsorptive voltammetry at carbon paste electrode using an electroactive cationic surfactant was examined. The adsorption state of the cationic surfactant in the complexes at CPE was estimated from the half‐height width of the oxidation waves. The half‐height width for poly(styrene sulfonate) was independent of the molecular weight, and was same as that for poly(vinyl sulfate). The half‐height width for heparin was broad and different from that of the vinyl polyanions. According to the analysis by Frumkin isotherm, the interaction between cationic surfactants was attractive in heparin complex at CPE, however, in the vinyl polyanion complexes at CPE the interaction was non‐cooperative as that predicted with the Langmuir isotherm. In spite of the same adsorption state, the concentration dependency of the peak current for poly(styrene sulfonate) was quite different from that for poly(vinyl sulfate). The concentration dependence indicated the reactive property of each polyanion on the association with the cationic surfactant in aqueous solution.     

Electrokinetic characterization of poly(acrylic acid) and poly(ethylene oxide) brushes in aqueous electrolyte solutions

Surfaces carrying hydrophilic polymer brushes were prepared from poly(styrene)-poly(acrylic acid) and poly(styrene)-poly(ethylene oxide) diblock copolymers, respectively, using a Langmuir-Blodgett technique and employing poly(styrene)-coated planar glass as substrates. The electrical properties of these surfaces in aqueous electrolyte were analyzed as a function of pH and KCl concentration using streaming potential/streaming current measurements. From these data, both the zeta potential and the surface conductivity could be obtained. The poly(acrylic acid) brushes are charged due to the dissociation of carboxylic acid groups and give theoretical surface potentials of -160 mV at full dissociation in 10(-)(3) M solutions. The surface conductivity of these brushes is enormous under these conditions, accounting for more than 93% of the total measured surface conductivity. However, the mobility of the ions within the brush was estimated from the density of the carboxylic acid groups and the surface conductivity data to be only about 14% of that of free ions. The poly(ethylene oxide) (PEO) brushes effectively screen the charge of the underlying substrate, giving a very low zeta potential except when the ionic strength is very low. From the data, a hydrodynamic layer thickness of the PEO brushes could be estimated which is in good agreement with independent experiments (neutron reflectivity) and theoretical estimates. The surface conductivity in this system was slightly lower than that of the polystyren substrate. This also indicates that no significant amount of preferentially, i.e., nonelectrostatically attracted, ions taken up in the brush.     

Synthesis of poly(styrene sulfonate) brushes.

Dense poly(styrene sulfonate sodium salt) brushes were prepared on silicone wafers using a two-step procedure: polystyrene (PS) chains, terminated by a reactive trichlorosilane group, were first covalently grafted, and then the PS brush was converted to a poly(styrene sulfonate) brush by a soft sulfonation reaction. Ellipsometry and infrared spectroscopy in ATR were used to characterize the samples and to optimize the procedure: in particular, the sulfonation was shown to be homogeneous along the chain backbone and the neutralization complete. In some cases, the polymer layer revealed to be quite fragile: the chains were pulled out of the brush. A consolidation treatment which consisted in grafting oligomers inbetween the long PS chains significantly increased the robustness of the layer. This might be relevant for industrial applications.     

Interaction of poly(styrene sulfonate) with polycations carrying charges in the chain backbone

The interaction between sodium poly(styrene sulfonate) (NaSS) and side-chain charged polycation polymer (pendent type) or main-chain charged polycation polymer (integral type) has been studied. It was found that the polyion complex (the reaction product of these polyelectrolytes) of pendent–pendent type has an equimolar composition at any mixing ratio of two component polymers. However, a polyion complex of integral–pendent type can form a water-soluble complex with a ratio of [polycation]/[polyanion] = 1/3, in addition to a complex with a equimolar composition. The mechanism of formation of this specific complex is discussed.     

Reduction of silver ions to silver with polyaniline/poly(vinyl alcohol) cryogels and aerogels

The macroporous conducting polymer cryogels were prepared by the oxidation of aniline hydrochloride in the frozen aqueous solutions of poly(vinyl alcohol) at ? 24 °C. Corresponding polyaniline aerogels supported with poly(vinyl alcohol) have been obtained after thawing of cryogels followed by freeze-drying. Silver was deposited on the composites using the ability of polyaniline to reduce silver ions after the immersion in silver nitrate solutions. Swollen cryogels were coated only on the surface with macroscopic silver particles due to the closed-pore structure in cryogels and limited penetration of silver ions into macropores. The diffusion of silver ions to freeze-dried aerogels was better and further improved by vacuum treatment. Silver microcubes were produced in the pores, the weight fraction of silver in dry composites being typically several per cent, a maximum 13 wt%. The conductivity of the aerogels compressed to pellets depended on the processing and the highest value was 0.27 S cm^?1. The aerogels containing silver were characterized in detail with Raman spectroscopy.     

Immobilisation of lactate dehydrogenase on poly(aniline)-poly(acrylate) and poly(aniline)-poly(vinyl sulphonate) films for use in a lactate biosensor

The immobilisation of enzymes on an electrode surface, in such a manner that they retain both substrate specificity and high levels of catalytic activity, is of great importance in bioelectrochemistry. This includes areas such as the development of enzyme-catalysed fuel cell electrodes, biosensors and other biotechnological applications. We have investigated the catalytic activity of hexahistidine tagged variants of lactate dehydrogenase (EC 1.1.1.27) from the thermophile Bacillus stearothermophilus both in solution and when immobilised on poly(aniline)-poly(acrylate) (PANi-PAA) or poly(aniline)-poly(vinyl sulphonate) (PANi-PVS) composite films. Both the C- and N-terminally tagged enzymes are readily immobilised on the modified electrode and catalyse the conversion of lactate and NAD⁺ to pyruvate and NADH. The NADH that is generated can be readily oxidised at the PANi-modified electrode surface.In solution, the activity of the C-tagged enzyme (LDH-CHis) was some 30% less that of the wild-type under comparable conditions, whereas the N-tagged enzyme was found to possess essentially the same activity as the wild-type. However, when the enzymes were immobilised on PANi-PAA and PANi-PVS the C-tagged enzyme films showed a higher NADH-dependent current than the wild-type LDH whilst the N-tagged enzyme had the highest of the three. In addition, the C-tagged enzyme film appeared more stable than the wild-type LDH-PANi film. A novel immobilisation chemistry of the enzyme is proposed to account for these observations.     

Electrochemically modulated permeability of poly(aniline) and composite poly(aniline)-poly(styrenesulfonate) membranes

The influence of oxidation state on the permeability of several probe molecules through conducting polymer membranes comprising composites of poly(aniline) and poly(styrenesulfonate) was examined in aqueous solution. Pure poly(aniline) membranes displayed a characteristic increase in permeability between reduced and half-oxidized states for neutrally charged phenol and negatively charged 4-hydroxybenzenesulfonate. In contrast, positively charged pyridine experienced decreased permeability through the membrane when poly(aniline) was switched from the reduced to the half-oxidized state. This behavior can be explained by a combination of oxidation-induced film swelling and the anion-exchange character of the positively charged membrane. The membrane composition was modified to include a fixed negative charge by the addition of poly(styrenesulfonate) during synthesis. The incorporation of this negatively charged component introduced cation-exchange character to the film and substantially reduced membrane permeability to 4-hydroxybenzenesulfonate in both oxidation states. In addition, increasing the fraction of poly(styrenesulfonate) in the membrane served to decrease film permeability for all species because of a densification of the membrane. This work demonstrates how both film composition and oxidation state can be used to tune the permeability of conducting polymer membranes.     

Ascorbate amperometric determination using conducting copolymers from aniline and N-(3-propane sulfonic acid)aniline

The sequential electrochemical polymerization of aniline and N-(3-propane sulfonic acid)aniline (PSA) is proposed to construct a sensor able to detect ascorbate at physiological conditions. Compared to poly(aniline) modified electrode, a device with improved conducting and electrochemical properties at neutral pH is obtained. The electrochemical copolymerization of the same starting materials is also carried out. For a PSA:aniline ratio of 10:90, a polymer with a similar electrochemical behavior to the one grown in the sequential mode is observed.The detection of ascorbate was tested for both configurations at pH 7.2, the modified electrode is able to determine ascorbate at 0 mV versus Ag/AgCl; an optimized sensor constructed by sequential polymerization can easily detect ascorbate concentrations with a detection limit of 2.2 μM. Uric acid and dopamine does not interfere in the ascorbate determination.     

Effects of the structure of anionic polyelectrolytes on surface potentials of their aggregates in water

The surface potential, ψ in mV, was determined for the following polyelectrolytes and co-polyelectrolytes in aqueous solution: sodium poly(styrene sulfonate); sodium poly(vinyl sulfonate); poly(vinyl alcohol-co-55% sodium vinyl sulfate); poly(methylmethacrylate-co-40% sodium styrene sulfonate); poly (methylmethacrylate-co-60% sodium styrene sulfonate); poly(styrene-co-56% styrene sulfonate); and poly(styrene-co-80% styrene sulfonate). For comparison, the surface potentials of aqueous sodium dodecyl sulfate and sodium dodecylbenzene sulfonate micelles were also determined. The dyes neutral red and safranine-T were used as indicators. ThepKa of the former was calculated from the Henderson-Hasselbach equation, using UV-VIS spectroscopy to determine the concentration of protonated ground state as a function of pH. The surface potential of the aggregates was culculated from the equation: $$pKa_{\text{i}} = pKa_0 - {{F\Psi } \mathord{\left/ {\vphantom {{F\Psi } {2.3RT}}} \right. \kern-\nulldelimiterspace} {2.3RT}}$$ wherepKa _i andpKa _o refer to the indicatorpKa in the presence of charged and nonionic interfaces, respectively, and the other terms have their usual meaning. The protonation kinetics of the triplet state of safranine-T (measured from the decay of its transient absorption at 830 nm) was used to determine hydronium ion concentrations at aggregate interfaces, and the corresponding surface potentials were calculated from: $$a_{{\text{Hi}}} = a_{{\text{Haq}}} \times \exp \left( {{{ - F\Psi } \mathord{\left/ {\vphantom {{ - F\Psi } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)$$ wherea _Hi anda _Haq refer to the hydronium ion activity at the aggregate interface, and in bulk water, respectively. Surface potentials determined by both techniques were in excellent agreement. Values of ψ were found to depend on the structure of the polyelectrolyte, sodium poly(styrene sulfonate) versus sodium poly(vinyl sulfonate) and, for the same type of co-polyelectrolyte, on the percentage of charged monomer.     

Differences in binding of a cationic surfactant to cross-linked sodium poly(acrylate) and sodium poly(styrene sulfonate) studied by Raman spectroscopy

Raman spectroscopy has been used to investigate the structure of gel-surfactant complexes. Cross-linked sodium poly(acrylate) and sodium poly(styrene sulfonate) were immersed in solutions of the cationic surfactant dodecyl trimethylammonium bromide. During the deswelling process, two distinct regions could be observed for both types of gels. Looking at the Raman spectra, however, for the poly(styrene sulfonate), the surfactant could be found throughout the gel particle, whereas for poly(acrylate), essentially all the surfactant was bound in a surface layer.     

Optimization of the thickness of a conducting polymer, polyaniline, deposited on the surface of poly(vinyl chloride) membranes: a new way to improve their potentiometric response

Repeated depositions of polyaniline (PANI) have been used to control the thickness of the polymeric film deposited on poly(vinyl chloride) (PVC) membrane surface. The oxidation of aniline was carried out in a dispersion mode, i.e. in the presence of poly(N-vinylpyrrolidone) (PVP). Two kinds of PVC were used for this purpose: a non-plasticized PVC for the study of PANI deposition and PVC, plasticized with nitrophenyl octyl ether (NPOE), as a prototype of a liquid membrane electrode. The results of UV-visible and FTIR spectroscopies and electron microscopy showed that (1) the film thickness increased by about equal increments of ∼40 nm after each polymerization, and (2) the interface with PVC was constituted by PANI film and adhering PANI-PVP colloidal particles.The various thicknesses of the deposited PANI films affected the potentiometric response of the NPOE/PVC membrane with and without an anion-exchanger. The potentiometric anionic response was observed with a minimal thickness of PANI film on the blank NPOE/PVC membrane. Sensitivity of the PANI film to pH occurred only with a blank NPOE/PVC membrane coated with a thick polymeric film, while it was strongly suppressed by the presence of a lipophilic anion-exchanger, tridodecylmethylammonium chloride (TDDMACl), in the membrane, regardless of the thickness of the polymer film. The thickness of the PANI film did not affect the anionic selectivity pattern of TDDMACl-based membranes to any great extent, but its presence improved and stabilized their potentiometric characteristics (sensitivity, linear-response range).     

Laser reflectometry to investigate adsorption–desorption of poly(styrene sulfonate) onto polyamide 6.6

The adsorption of poly(styrene sulfonate) (PSS) on polyamide 6-6 was investigated using fixed angle laser reflectometry. The appropriate polyamide film thickness for an accurate analysis was first determined theoretically. Polyamide films were further prepared at controlled thickness using dip-coating processes and characterized. The adsorption of PSS was measured at pH 3 on dip-coated films as a function of time and polymer concentration. The adsorption rate at very low polymer coverage revealed diffusion limited adsorption. At and above pH 10, the PSS adsorption/desorption was difficult to evaluate. At and above pH 11.5, the hydrolysis of polyamide produced artifacts that prevent any meaningful measurements. This work showed that reflectometry is an interesting analytical tool in the in situ study of the functionalization of organic materials and to investigate the stability of the films produced.     

SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTIVITY OF N,N''-BIS(3-ALLYL SALICYLIDENE)ETHYLENEDIAMINE COBALT(II) SCHIFF BASE COMPLEX ANCHORED ON A NEW POLYMER SUPPORT

A new chelating polymer support has been prepared by suspension copolymeriz a tion of synthesized N,N'-bis(3-allyl salicylidene)ethylenediamine monomer Schiff base (N,N'-BSEDA) with styrene (St) and divinylbenzene (DVB) using azobisisobutyronitrile (AIBN) as initiator in the presence of poly(vinyl alcohol). The content and complexation ability of monomer Schiff base (N,N'-BSEDA) for cobalt(II) ions in prepared crosslinked polymer beads have shown dependence on the amount of DVB used in reaction mixture. The amount of monomer Schiff base (N,N'-BSEDA) in crosslinked beads showed a substantial decreasing trend at high concentration of DVB in the reaction mixture (＞ 1.5 mol dm-3), hence the efficiency of complexation (EC%) and cobalt(II) ion loading (EL%) of polymer beads showed a decreasing trend. The structure of monomer Schiff base (N,N'-BSEDA) and its cobalt(II) complex on polymer support was elucidated by IR, UV and magnetic measurements. The catalytic activity of polymer bound cobalt(Ⅱ) Schiff base complex was evaluated by analyzing kinetic data of decomposition of hydrogen peroxide in the presence of either supported cobalt (II) complex or free cobalt(II) complex. The activation energy for the decomposition of hydrogen peroxide by polymer supported cobalt(II)complex was found to be low (33.37 kJ mol-l) in comparison with unsupported cobalt(II) complex (56.35 kJ mol-1). On the basis of experimental observations, reaction steps are proposed and a suitable rate expression derived.     

Adsorption of charged diblock copolymers on porous silica

Block copolymers of styrene and 2-vinylpyridine of different molecular weights were synthesized and chemically modified to poly(vinyl pyridine)/poly(styrene sulfonate) or polystyrene/poly(2-vinyl pyridinium) salts. Adsorption on “Spherosil” silica with a high specific surface area was performed from aqueous solutions of polyelectrolyte copolymers or from noncharged copolymer in an organic medium and subsequent sulfonation or quaternization in the adsorbed state. The adsorption mechanism was studied under various solvent conditions to give silica maximal ion-exchange properties. Modification of silica resulted in a highly stable coated material which combines the mechanical properties of the porous beads and the ion-exchange properties of the “supported” and “pellicular” ion-exchangers and should have potential use in chromatography.     

Studies on the kinetics of ascorbate oxidation at a ruthenium oxide hexacyanoferrate modified electrode towards the detection at microenvironments

The electrocatalytic oxidation of ascorbate on a ruthenium oxide hexacyanoferrate (RuOHCF) glassy carbon (GC) modified electrode was investigated at pH 6.9 by using rotating disc electrode (RDE) voltammetry. The influence of the systematic variation of rotation rate, film thickness, ascorbate concentration and the electrode potential indicated that the rate of cross-chemical reaction between Ru(III) centres immobilized into the film and ascorbate controls the overall process. The kinetic regime may be classified as a Sk″ mechanism and the second order rate constant for the surface electrocatalytic reaction was found to be 1.56 × 10⁻³ mol⁻¹ L¹ s⁻¹ cm. A carbon fibre microelectrode modified with the RuOHCF film was successfully used as an amperometric sensor to monitor the ascorbate diffusion in a simulated microenvironment experiment.