Influence of silanization on voltammetry at electrodes modified with silica films of controlled porosity formed by electrochemically initiated sol-gel processing

Silica sol-gel (SG) films with templated pores were deposited on glassy carbon (GC) electrodes by an electrochemically initiated process. Generation-4 poly(amidoamine), PAMAM, dendrimer was included in the tetraethoxysilane precursor to facilitate pore formation. The PAMAM adsorbs to the GC, which blocks SG formation at those sites on the electrode. The pore size was 10 ± 5 nm. After removal of the PAMAM, cyclic voltammetry of Fe(CN)₆ ³⁻ and Ru(NH₃)₆ ³⁺ at pH 6.2 showed that the residual negative charge on the silica attenuated the current for the former and increased the current for the latter, presumably by electrostatic repulsion and ion-exchange preconcentration, respectively. This premise was supported by repeating the measurements at the isoelectric point. Methylation of the silanol sites was used to eliminate the charge of the SG. At the end-capped SG, the voltammetry of Fe(CN)₆ ³⁻ and Ru(NH₃)₆ ³⁺ yielded currents that were independent of pH over the range 2.1 to 7.2. Circumventing the need for the silanization by using (3-glycidyloxypropyl)trimethoxysilane as the sol-gel precursor failed because the oxygen plasma treatment to remove the PAMAM attacked the organically modified sol-gel backbone. The resulting modified electrode mitigated the influence of proteins on the voltammetry of test species and stabilized functionalize nanoparticle catalysts under hydrodynamic conditions.

     

Electrochemical Studies of Thiol Self‐Assembled Monolayers at a Heated Gold‐Wire Microelectrode

Mercaptoundecanoic acid (MUA) and glutathione (GSH) self‐assembled monolayers were prepared on gold‐ wire microelectrode. Cyclic voltammetry was used to investigate the influence of temperature on electrochemical behaviors of Fe(CN)₆^3?/4? and Ru(NH₃)₆^3+/2+ at these SAMs modified electrodes in aqueous solution. It is found that temperature shows great influence on electron transfer (ET) and mass transport (MT) for the two SAMs modified electrodes and the influence of temperature depends on the charge properties of the redox couples and terminal groups of SAMs and the structure of the monolayer on gold surface. The temperature can greatly increase MT rate of Fe(CN)₆^3?/4? at both MUA and GSH modified electrodes. However, the increased MT rate doesn't have any effect on the CV's for Fe(CN)₆^3?/4? /MUA system. For Ru(NH₃)₆^3+/2+ , temperature can greatly improve the electrochemical reaction in both MUA and GSH modified electrodes, which is ascribed to temperature‐induced diffusion and convection and the electrostatic interaction between Ru(NH₃)₆^3+/2+ and negatively charged carboxyl groups on the electrode surface.     

Low Temperature Synthesis of Zeolite Films on Glassy Carbon: Towards Designing Molecularly Selective Electrochemical Devices

Faujasite‐type zeolite films have been grown on glassy carbon electrode surfaces embedded in an epoxy resin matrix by a quasi ambient temperature hydrothermal synthesis. The resulting zeolite modified electrodes are mechanically stable and provide an advantageous combination of electrochemical detection with charge and size selectivities at the molecular level, as demonstrated with the aid of some model electroactive probes or analytes (Ru(NH₃)₆³⁺, Fe(CN)₆^3?, Ru(bpy)₃²⁺, dopamine, ascorbic acid). To act efficiently as a physical molecular sieve barrier between the electrode surface and the external solution, these films must have a thickness of about 0.7 μm. These results open the door for further development of molecular sieving electrochemistry.     

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

Modification of electrodes with nanometer-scale organically modified silica films with pore diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano cross-links or gold nanoparticles protected by dirhodium-substituted phosphomolybdate (AuNP-Rh₂PMo₁₁), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. Ten-nanometer pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH₃)₃SiOCH₃ sol. Fifty-nanometer pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH₃)₃SiOCH₃ sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)₆ ^3? and Ru(NH₃)₆ ³⁺ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh₂PMo₁₁ therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.     

Kinetic Study of the Ru(II) Catalyzed Oxidation of Pentacyanoferrate(ll) Complexes by Peroxydisulfate

The oxidation reactions of Fe(CN)₅L^3? (L = 4-ampy, py, dpa) complexes by S₂O₈^2? were catalyzed upon the addition of a trace amount of Ru(NH₃)₅L′²⁺ (L′ = pz, py or dcb) complex, and the reaction becomes zero-order in Fe(II). The reaction time is ～10² fold faster than the simple Fe(CN)₅L^3?-S₂O₈^2? system. The mechanism of this Ru(II) catalyzed redox reaction is proposed as Ru(NH₃)₅L′²⁺ + 1/2 S₂O₈^2? → Ru(NH₃)₅L′³⁺ + SO₄^2? Ru(NH₃)₅L′³⁺ + Fe(CN)₅L^3? ? Ru(NH₃)₅L′²⁺ + Fe(CN)₅L^2?     

Mixed Valence Chemistry of Pyrimidine Bridged Binuclear Complex of Pentacyanoferrate and Pentaammineruthenium

The pyrimidine bridged binuclear complex (CN)₅FepymRu(NH₃)₅- (I) was prepared in aqueous solution by mixing cquimolar of Fe(CN)₅OH₂^3? and Ru(NH₃)₅pym²⁺. Its mixed valence state molecule (CN)₅FepymRu(NH₃)₅(II) was obtained upon oxidation of I by one equivalent of peroxydisulfate ion. Both binuclear complexes and corresponding Fe(II) and Ru(II) mononuclear complexes displayed a metal-to-ligand charge transfer absorption in 400–450 nm region. Rate constants of formation and dissociation of I and II were measured, and the values of k_f (?10³M^?1s^?1) and k_d (?10^?3-10^?4 s^?1) were consistent with kinetic results expected for the substitution of Fe(CN)₅OH₂^3? with di- and trivalent ligands. Cyclic voltammetry of I exhibited two one-electron steps of oxidation corresponding to [III, L, II] + e → [II, L, II] and [III, L, III] + e → [III, L, II], respectively. The mixed valence binuclear complex II showed an intervalence band at 955 nm with a molar extinction coefficient 5.80 × 10² M^?1cm^?1 and a half-width 5100 cm^?l. The properties of the IT band conform to Hush's theory. Spectroscopic, electrochemical and kinetic results of II suggest that the mixed valence complex features a trapped - valence formulation with localized oxidation states of Fe(II) and Ru(III).     

Fabrication of Chitosan‐Multiwall Carbon Nanotube Nanocomposite Containing Ferri/Ferrocyanide: Application for Simultaneous Detection of D‐Penicillamine and Tryptophan

We report a simple and effective strategy for fabrication of the nanocomposite containing chitosan (CS) and multiwall carbon nanotube (MWNT) coated on a glassy carbon electrode (GCE). The characterization of the modified electrode (CS‐MWNT/GC) was carried out using scanning electron microscopy (SEM) and UV–vis absorption spectroscopy. The electrochemical behavior of CS‐MWNT/GC electrode was investigated and compared with the electrochemical behavior of chitosan modified GC (CS/GC), multiwalled carbon nanotube modified GC (MWNT/GC) and unmodified GC using cyclic voltammetry (CV) and electron impedance spectroscopy (EIS). The chitosan films are electrochemically inactive; similar background charging currents are observed at bare GC. The chitosan films are permeable to anionic Fe(CN)₆^3?/4? (FC) redox couple. Electrochemical parameters, including apparent diffusion coefficient for the Fe(CN)₆^3?/4? redox probe at FC/CS‐MWNT/GC electrode is comparable to values reported for cast chitosan films. This modified electrode also showed electrocatalytic effect for the simultaneous determination of D‐penicillamine (D‐PA) and tryptophan (Trp). The detection limit of 0.9 μM and 4.0 μM for D‐PA and Trp, respectively, makes this nanocomposite very suitable for determination of them with good sensitivity.     

Electrostatic bending and outer-sphere intervalence transfer in a flexible ligand-bridged ruthenium(III)-iron(II) complex

Abstract

In the mixed-valence complex [Ru^III(NH₃)₅(μ-dpypn)Fe^II(CN)₅] with the flexible bridging ligand 1,3-di(4-pyridyl)propane (dpypn), electrostatic interactions between the {Ru(NH₃)₅}³⁺ and {Fe(CN)₅}^3? moieties drive a strong bending of dpypn and approximation of the Ru^III and Fe^II centers, from which the enhanced electronic coupling between metal ions produces an intense intervalence-transfer absorption in the near-infrared region. Density functional theory calculations corroborate both the electrostatic bending in this heterobinuclear complex and a linear geometry in the homobinuclear counterparts [Ru(NH₃)₅(μ-dpypn)Ru(NH₃)₅]⁵⁺ and [Fe(CN)₅(μ-dpypn)Fe(CN)₅]^5?, for which no evidence of electronic coupling was found because of the separation between metal centers. Furthermore, the heterobinuclear species formed an inclusion complex with β-cyclodextrin where the imposed linear geometry prevents significant electronic coupling and intervalence charge transfer between the Ru^III and Fe^II centers.     

The Effect of Ionic Liquid Covalent Bonding to Sol‐Gel Processed Film on Ion Accumulation and Transfer

Accumulation of electroactive anions into a silicate film with covalently bonded room temperature ionic liquid film deposited on an indium tin oxide electrode was studied and compared with an electrode modified with an unconfined room temperature ionic liquid. A thin film containing imidazolium cationic groups was obtained by sol‐gel processing of the ionic liquid precursor 1‐methyl‐3‐(3‐trimethoxysilylpropyl)imidazolium bis(trifluoromethylsulfonyl)imide together with tetramethylorthosilicate on the electrode surface. Profilometry shows that the obtained film is not smooth and its approximate thickness is above 1 μm. It is to some extent permeable for a neutral redox probe – 1,1′‐ferrocene dimethanol. However, it acts as a sponge for electroactive ions like Fe(CN)₆^3?, Fe(CN)₆^4? and IrCl₆^3?. This effect can be traced by cyclic voltammetry down to a concentration equal to 10^?7 mol dm^?3. Some accumulation of the redox active ions also occurs at the electrode modified with the ionic liquid precursor, but the voltammetric signal is significantly smaller compare with the bare electrode. The electrochemical oxidation of the redox liquid t‐butyloferrocene deposited on silicate confined ionic liquid film is followed by the expulsion of the electrogenerated cation into an aqueous solution. On the other hand, the voltammetry obtained with the electrode modified with t‐butyloferrocene solution in the ionic liquid precursor exhibits anion sensitive voltammetry. This is explained by anion insertion into the unconfined ionic liquid deposit following t‐butylferricinium cation formation.     

Zero Current Potentiometry for Measuring the Interface Potential at the Electrode/Solution Interface. Theoretical and Experimental Study

A novel electrochemical approach has been proposed to measure the interface potential at the electrode/solution interface based on reconstructing the three‐electrode system of a potentiostat. In this work, the method was investigated both theoretically and experimentally. Mathematical expressions, describing current? potential characteristics, were derived. Zero current potential E_zcp was defined as the potential at which the current is zero based on linear sweep voltammetry, and was determined from the I? E curve to measure the interface potential. The experimental results obtained with the couples Fe(CN)₆^3?/Fe(CN)₆^4? and Co(NH₃)₆³⁺/Co(NH₃)₆²⁺ as examples agreed well with the theory. The proposed approach exhibits an excellent performance for measuring the interface potential due to the advantages of rapidity, high stability and accuracy.     

A layer-by-layer assembly label-free electrochemical immunosensor for the detection of microcystin-LR based on CHIT/PAMAM dendrimer/silver nanocubes

Utilising the affinity and high combination ability between silver nanocubes and amino group (–NH₂), a novel electrochemical immunosensor was constructed for the ultrasensitive detection of microcystin-LR (MC-LR) based on G4-polyamidoamine (PAMAM) dendrimer and Ag nanocubes as immobilised substrate of anti-MC-LR. G4-PAMAM dendrimers were covalently bound on the chitosan (CHIT) – modified electrode by glutaraldehyde (GA), providing abundant amino groups to absorb much more Ag nanocubes comparing without using PAMAM. Subsequently, antibodies of MC-LR were immobilised with highly dense through Ag-NH₂. K₃Fe(CN)₆/K₄Fe(CN)₆ was used as electroactive redox probe. Ag nanocubes/PAMAM can enhance the antibody loading amount, which would bind more MC-LR and hinder the electron transfer of K₃Fe(CN)₆/K₄Fe(CN)₆. Differential pulse voltammetry (DPV) was employed to evaluate the analytical performance of the fabricated signal-off immunosensor. The response current had negative correlation with the concentration of MC-LR. The linear range covered was from 0.05 ng/mL to 25 μg/mL with detection limit (DL) of 0.017 ng/mL at 3σ. The proposed approach showed high specificity for the detection of MC-LR, with acceptable reproducibility, stability and reliability. Compared with the enzyme-linked immunoassay (ELISA) method by analyzing real water samples from Dian Lake, this immunosensor revealed acceptable accuracy with a relative error of 12.7%, indicating a potential alternative method for MC-LR detection in water sample.     

Titanium Carbide Thin‐Film Electrodes: Characterization and Evaluation as Working Electrodes

Titanium carbide (TiC) polycrystalline thin films, obtained by a hybrid chemical vapor deposition/powder flowing technique, were characterized and used to assemble working electrodes. The potential window and the electrochemistry of standard redox couples ([Ru(NH₃)₆]³⁺, [Fe(CN)₆]^3?) have been investigated in cyclic voltammetry, demonstrating a behavior similar to glassy carbon electrodes. The quinone (Q)/hydroquinone(H₂Q) redox couple presented an interesting quasireversible behavior(E_p=0.07 mV) , confirmed also for other quinones.     

A Novel Three‐Electrode System Fabricated on Polymethyl Methacrylate for On‐Chip Electrochemical Detection

A new strategy of three‐electrode system fabrication in polymer‐based microfluidic systems is described here. Standard lithography, hot embossing and UV‐assisted thermal bonding were employed for fabrication and assembly of the microfluidic chip. For the electrode design the gold working (WE) and counter electrodes (CE) are placed inside a main channel through which the sample solution passes. A silver reference electrode (RE) is embedded in a small side channel containing KCl solution that is continuously pushed into the main channel. In the present work, the overall electrochemical set up and its microfabrication is described. Conditions including silver ion concentration, cyclic voltammetry (CV) settings, and the flow rate of KCl solution in the RE channel were optimized. The electrochemical performance of the three‐electrode system was evaluated by CV and also by amperometric oxidation of ferro hexacyanide ([Fe(CN)₆]^4?) and ruthenium bipyridyl ([Ru(bipy)₃]²⁺) at 400 mV and 1200 mV, respectively. CV analysis using ferri/ferro hexacyanide showed a stable, quasi‐reversible redox reaction at the electrodes with 96 mV peak separation and an anodic/cathodic peak ratio of 1. Amperometric analysis of the electrochemical species resulted in linear correlation between analyte concentration and current response in the range of 0.5–15 µM for [Fe(CN)₆]^4?, and 0–1000 µM for [Ru(bipy)₃]²⁺. Upon the given experimental conditions, the limit of detection was found to be 3.15 µM and 24.83 µM for [Fe(CN)₆]^4? and [Ru(bipy)₃]²⁺, respectively. As a fully integrated three‐electrode system that is fabricated on polymer substrates, it has great applications in microfluidic‐based systems requiring stable electrochemical detection.     

Carbon Nanotube Immobilized Electrode Using Amphiphilic Phospholipid Polymer with Anti‐fouling and Dispersion Property for Electrochemical Analysis

A carbon nanotube (CNT)‐modified electrode was fabricated by dropping a dispersion of multi‐walled CNTs in water‐soluble and amphiphilic phospholipid polymer with both dispersing ability and anti‐biofouling property onto a Au electrode. A poly(2‐methacryloyloxyethyl phosphorylcholine‐co‐n‐butyl methacrylate) (PMB) composed from 50 mol% of 2‐methacryloxylethyl phosphorylcholine and 50 mol% of n‐butyl methacrylate (PMB50) was used as dispersing reagent for CNTs. The dispersion of water‐insoluble material by PMB50 and its antifouling effects in electrochemical analysis were investigated. The CNT‐modified electrode showed an anodic peak potential that was shifted negatively and an increase in the current value for the electrolytic oxidation of nicotinamide adenine dinucleotide. In addition, the charge on PMB50 did not inhibit the electrochemical reaction of the redox compounds K₃[Fe(CN)₆], [Ru(NH₃)₆]Cl₃, and hydroxymethylferrocene. Cyclic voltammetry of K₃[Fe(CN)₆] in 4 % bovine serum albumin (BSA) using a bare Au electrode, the anodic peak current was reduced to 47 % of that without BSA. In contrast, the antifouling effect of the PMB50‐coated electrode meant that the current was only reduced to 70 % of that without BSA.     

Changes of electrochemical responses of the bulk solution species by thermotropic permeability of liquid crystalline membranes coated on electrodes

Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)^3?₆ ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)^—₆ at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)^3?₆ in a bulk solution was examined in order to understand the transport process of Fe(CN)^?3₆ through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)^3?₆ within the membrane was found to obey Fick's Law.     

Enzyme-free impedimetric glucose sensor based on gold nanoparticles/polyaniline composite film

A non-enzymatic impedimetric glucose sensor was fabricated based on the adsorption of gold nanoparticles (GNPs) onto conductive polyaniline (PANI)-modified glassy carbon electrode (GCE). The modified electrode (GCE/PANI/GNPs) was characterized by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). The determination of glucose concentration was based on the measurement of EIS with the mediation of electron transfer by ferricyanide ([Fe(CN)₆]^3?). The [Fe(CN)₆]^3? is reduced to ferrocyanide ([Fe(CN)₆]^4?), which in turn is oxidized at GCE/PANI/GNPs. An increase in the glucose concentration results in an increase in the diffusion current density of the [Fe(CN)₆]^4? oxidation, which corresponds to a decrease in the faradaic charge transfer resistance (R _ct). A wide linear concentration range from 0.3 to 10 mM with a lower detection limit of 0.1 mM for glucose was obtained. The proposed sensor shows high sensitivity, good reproducibility, and stability. In addition, the sensor exhibits no interference from common interfering substances such as ascorbic acid, acetaminophen, and uric acid.     

Thionicotinamide SAM on Gold: Adsorption Studies and Electroactivity

STM and impedance results of the self‐assembled monolayer (SAM) formed with thionicotinamide (TNA) on gold indicate the presence of defects that increase with the immersion time of the electrode in the TNA solution affecting the SAM electroactivity toward the electron transfer reaction of the cytochrome c metalloprotein and [Fe(CN)₆]^4? and [Ru(NH₃)₆]³⁺ complexes. It was observed that this electroactivity was also affected by the pH of the electrolyte solution. SERS and STM data indicate sulfur coordination to the surface with contribution of the NH₂ group. From the dependence of the TNA surface coverage on the temperature and concentration in solution, thermodynamic parameters of adsorption were determined.     

Self‐assembly of p‐Aminothiophenol on Gold Surface: Application for Impedimetric and Potentiometric Sensing of Cobalt (II) Ions – A Comparative Study

Cobalt, despite an essential biological element, imposes threat to humans when exposed to high concentration or even to low concentration for long term which demands the development of highly sensitive and selective analytical methods for its trace analysis. In the present work, self‐assembly of p‐aminothiophenol (p‐ATP) on gold surface (Au?ATP SAM) was carried out and for the first time, applied as a platform for impedimetric and potentiometric sensing of Co²⁺. Au?ATP SAM was characterized using electrochemical techniques: cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), in the presence of two redox probes: [Fe(CN)₆]^3?/4? and [Ru(NH₃)₆]^2+/3+ to evaluate associated passivating behaviour. Au?ATP SAM completely blocked [Fe(CN)₆]^3?/4? as compared to [Ru(NH₃)₆]^2+/3+ which may be attributed to inner‐sphere and outer‐sphere ET mechanisms, respectively. Au?ATP SAM was found to exhibit excellent sensitivity towards Co²⁺ in a wider concentration range from 1.0×10^?12 M to 1.0×10^?5 M (r²=0.963) at pH 5.5 with a detection limit of 6.0×10^?13 M and superior selectivity. Further, carbon paste electrode (CPE) was prepared by incorporating p‐ATP bound gold nanoparticles and explored for potentiometric sensing of Co²⁺ which exhibited Nernstian slope of 29.2±0.2 mV/dec in linear concentration range of 1.0×10^?6 M–1.0×10^?1 M (r²=0.971) with a detection limit of 8.0×10^?7 M. The proposed sensors were successfully applied for estimation of Co²⁺ content in water samples.     

Kinetic determination of hexacyanoferrates by their inhibition of an oscillating chemical reaction

A method for the kinetic determination of traces of hexacyanoferrate based on an oscillating chemical reaction is presented. In a Belousov-Zhabotinskii reaction system, by using a bromide ion-selective electrode, the amplitude decrease of the potentiometric oscillation is linearly proportional to the concentration of Fe(CN)^3?₆ [or Fe(CN)^4?₆] in the range 7 × 10^?8?5 × 10^?6 M. The relative standard deviation for 1 × 10^?6 M Fe(CN)^3?₆ is 2.7% (n = 6). Cyclic voltammetry was applied to study the mechanism of the proposed system. The procedure was utilized to determine hexacyanoferrates in silver plating and photographic solutions.     

Supramolecular microrods can be prepared by mixing aqueous Ru(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>Cl<Subscript>3</Subscript> and K<Subscript>3</Subscript>Fe(CN)<Subscript>6</Subscript> solutions at room temperature

This paper describes the ionic self-assembly method to fabricate supramolecular one-dimensional microrods in solution. Such microrods were formed in a one-step process through the mixing aqueous Ru(NH₃)₆Cl₃ and K₃Fe(CN)₃ solutions at room temperature. Chemical composition of the resulting structures, which are composed of from Fe(CN)₆⁴⁻ and Ru(NH₃)₆³⁺, was determined by energy-dispersed spectroscopy. The data show that the formation of microrods depends on the molar ratio and concentration of the reactants.