Quantitative Studies of Metal Ion Adsorption on a Chemically Modified Carbon Surface: Adsorption of Cd(II) and Hg(II) on Glutathione Modified Carbon

The adsorption behavior of model toxic metal cations namely Cd(II) and Hg(II) on carbon surfaces chemically modified by glutathione was investigated as a function of the concentration of Cd²⁺ and Hg²⁺ ions, time and the amount of modified carbon used. Square wave and linear sweep anodic stripping voltammetry was used to monitor the uptake of Cd(II) and Hg(II) ions respectively. Kinetic and adsorption isotherm studies reveal that both Cd(II) and Hg(II) ions undergo similar large adsorption with the modified glutathione carbon material (Glu‐carbon).     

The Convenient Determination of Palladium at a Solid Electrode via Adsorptive Stripping Voltammetry at a Glassy Carbon Electrode Modified with a Random Array of Mercury Nanodroplets

The detection of palladium using adsorptive stripping voltammetry reported by Wang et al. (J. Wang, K. Varughese Anal. Chim. Acta 1987, 199, 185 [3]) at a hanging mercury drop electrode is extended to a more convenient solid electrode. To this end a random array of 3.5×10⁸ mercury nanodroplets per cm² (65 nm average diameter) was electrodeposited on a glassy carbon substrate. Adsorptive stripping voltammetry was performed using 2×10^?4 M dimethylglyoxime as a chelating agent for the Pd(II) ion, with accumulation at ?0.20 V vs. SCE for 120 s and a linear detection range of 5–150 μM was determined with a limit of detection of 1.6 μM.     

Contrasting pKa of protonated bis(3-aminopropyl)-terminated polyethylene glycol "Jeffamine" and the associated thermodynamic parameters in solution and covalently attached to graphite surfaces

The pKa value of protonated Jeffamine (bis(3-aminopropyl) terminated polyethylene glycol) in solution and attached as a monolayer to graphite surfaces has been determined using potentiometric titration. The protonated Jeffamine was found to have a pKa value of 9.7 in solution at 25 degrees C, whereas this value decreases to 7.1 when it is attached to a graphite surface. Potentiometric titrations from 25 to 40 degrees C allowed us to determine the surface pKa of the protonated Jeffamine at each temperature studied and hence to determine the enthalpy, entropy and Gibbs energy changes associated with the deprotonation of the amino-terminated surface bound Jeffamine groups. It was found that the enthalpic contribution is negligibly small and the evaluation of these thermodynamic parameters controlling the shift in surface pKa value indicates that this process is controlled by entropic contribution arising from the ordering/disordering of solvent molecules at the carbon-water interface. This suggests that the long chain Jeffamine molecules are oriented on the carbon surface rather than existing in the bulk solution.     

Electroanalytical Exploitation of Nitroso Phenyl Modified Carbon‐Thiol Interactions: Application to the Low Voltage Determination of Thiols

The electrochemical generation of nitrosophenyl groups covalently attached to graphite powder (nitrosophenylcarbon) from carbon powder chemically modified with nitrophenyl groups and their subsequent reaction with thiols (glutathione, cysteine and homocysteine) has been investigated as a method by which the later can be quantified. The modified carbon powder was immobilized onto a basal plane pyrolytic graphite electrode and characterized by cyclic voltammetry by scanning between 1.0 V and ?1.0 V vs. SCE in phosphate buffer (pH 7). Square wave voltammetry (SWV) was used for the determination of thiols and the SWV parameters were optimized. The nitrosophenylcarbon is electrogenerated from nitrophenylcarbon and can chemically oxidize thiols to disulfides. Subsequent reduction of nitrosophenylcarbon to phenylhydroxylaminecarbon during the square wave voltammetric process leads to a decrease in the reductive current. This can be correlated to the concentration of thiol present within the medium. The cyclic voltammetric responses of basal plane pyrolytic graphite electrode, edge plane pyrolytic graphite electrode, glassy carbon electrode and boron‐doped diamond electrode in the direct oxidation of thiols were also investigated and all were found to have a significantly higher overpotential compared to the described method using nitrosophenylcarbon.     

A mechanistic investigation into the covalent chemical derivatisation of graphite and glassy carbon surfaces using aryldiazonium salts

Modification of carbon materials such as graphite and glassy carbon in bulk quantities using diazonium salts is developed. We used both 4‐nitrobenzenediazonium tetrafluoroborate and 1‐antharaquinonediazonium chloride to modify graphite and glassy carbon surfaces. Experiments were carried out in the presence and absence of hypophosphorous acid and the mechanism involved in both cases were studied using cyclic voltammetry. The observed peak potentials for both the 4‐nitrophenyl and 1‐anthraquinonyl modified materials were found to differ depending on whether or not the hypophosphorous acid reducing agent was used. In the absence of hypophosphorous acid the derivatisation reaction was inferred to go through a cationic intermediate, whilst in the presence of the hypophosphorous acid the mechanism likely involves either a purely radical intermediate or a mixture of radical and cationic species. Derivatisation experiments from 5 to 70°C allowed us to determine the optimum derivatisation temperature for both cases, in the presence and absence of hypophosphorous acid. Optimum temperature was 20°C for the former and 35°C for the later. Copyright © 2008 John Wiley & Sons, Ltd.     

Investigating the thermodynamic causes behind the anomalously large shifts in pKa values of benzoic acid-modified graphite and glassy carbon surfaces

The difference between the values of 4-carboxyphenyl groups, covalently attached to either graphite (BAcarbon) or glassy carbon (BA-GC) surfaces, and benzoic acid in solution is explored using potentiometric titration and cyclic voltammetry. In solution, benzoic acid has a pKa of 4.20 at 25 degrees C. However, the observed pKa value on the graphitic surfaces shows significant deviations, with BAcarbon exhibiting a large shift to higher pKa values (pKa = 6.45) in contrast to BA-GC, which is shifted to lower pKa values (pKa = 3.25). Potentiometric titrations at temperatures between 25 and 50 degrees C allowed us to determine the surface pKa of these materials at each temperature studied and hence to determine the enthalpy, entropy, and Gibbs' energy changes associated with the ionization of the carboxylic acid groups. It was found that the enthalpic contribution is negligible and that the changes in surface pKa values are entropically controlled. This suggests that solvent ordering/disordering around the interface strongly influences the observed pKa value, which then reflects the relative hydrophobicity/hydrophilicity of the different graphitic surfaces.