Electrochemical functionalization at anodic conditions of multi-walled carbon nanotubes with chlorodiphenylphosphine.

Covalent functionalization of multi-walled carbon nanotubes (MWCNTs) and oxidized MWCNTs (o-MWCNTs) with chlorodiphenylphosphine (Ph2PCl) has been studied by cyclic voltammetry in organic medium. Depending the upper potential limit used in the electrochemical functionalization, different amount of phosphorus incorporation n is obtained, as result of the formation of radical species during the electrochemical oxidation of the Ph2PCl. The electrochemical oxidation of Ph2PCl promotes the covalent attachment of diphenylphosphine-like structure on the carbon nanotube surface. At the same time, the incorporation of Cl on the carbon nanotubes is observed during the functionalization. Furthermore, the presence of oxygen surface groups on the MWCNTs provides a favorable attachment of the Ph2P∙+ species, which has promoted preferentially the formation of CP bonds, whereas the amount of Cl is reduced.

Pyrroloquinoline quinone-dependent glucose dehydrogenase bioelectrodes based on one-step electrochemical entrapment over single-wall carbon nanotubes.

Development of effective direct electron transfer is considered an interesting platform to obtain high performance bioelectrodes. Therefore, designing of scalable and cost-effective immobilization routes that promotes correct direct electrical contacting between the electrode material and the redox enzyme is still required. As we present here, electrochemical entrapment of pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on single-wall carbon nanotube (SWCNT)-modified electrodes was carried out in a single step during electrooxidation of para-aminophenyl phosphonic acid (4-APPA) to obtain active bioelectrodes. The adequate interaction between SWCNTs and the enzyme can be achieved by making use of phosphorus groups introduced during the electrochemical co-deposition of films, improving the electrocatalytic activity towards glucose oxidation. Two different procedures were investigated for electrode fabrication, namely the entrapment of reconstituted holoenzyme (PQQ-GDH) and the entrapment of apoenzyme (apo-GDH) followed by subsequent in situ reconstitution with the redox cofactor PQQ. In both cases, PQQ-GDH preserves its electrocatalytic activity towards glucose oxidation. Moreover, in comparison with a conventional drop-casting method, an important enhancement in sensitivity was obtained for glucose oxidation (981.7 ± 3.5 nA mM-1) using substantially lower amounts of enzyme and cofactor (PQQ). The single step electrochemical entrapment in presence of 4-APPA provides a simple method for the fabrication of enzymatic bioelectrodes.

Synthesis of Phosphorus-Containing Polyanilines by Electrochemical Copolymerization.

In this study, the phosphonation of a polyaniline (PANI) backbone was achieved in an acid medium by electrochemical methods using aminophenylphosphonic (APPA) monomers. This was done through the electrochemical copolymerization of aniline with either 2- or 4-aminophenylphosphonic acid. Stable, electroactive polymers were obtained after the oxidation of the monomers up to 1.35 V (reversible hydrogen electrode, RHE). X-ray photoelectron spectroscopy (XPS) results revealed that the position of the phosphonic group in the aromatic ring of the monomer affected the amount of phosphorus incorporated into the copolymer. In addition, the redox transitions of the copolymers were examined by in situ Fourier-transform infrared (FTIR) spectroscopy, and it was concluded that their electroactive structures were analogous to those of PANI. From the APPA monomers it was possible to synthesize, in a controlled manner, polymeric materials with significant amounts of phosphorus in their structure through copolymerization with PANI.

Carbon Nanotubes Modified With Au for Electrochemical Detection of Prostate Specific Antigen: Effect of Au Nanoparticle Size Distribution.

Different functionalized Multi-Wall Carbon Nanotube and gold nanoparticles (AuNPs) were synthesized as biosensor electrodes. These materials have been applied to the detection of the Prostate Specific Antigen (PSA). The synthesis of AuNPs was carried out using polyvinylpyrrolidone (PVP) as protecting agent. The PVP/Au molar ratio (0.5 and 50) controls the nanoparticle size distribution, obtaining a wide and narrow distribution with an average diameter of 9.5 and 6.6 nm, respectively. Nanoparticle size distribution shows an important effect in the electrochemical performance of the biosensor, increasing the electrochemical active surface area (EASA) and promoting the electron-transfer from the redox probe (Ferrocene/Ferrocenium) to the electrode. Furthermore, a narrow and small nanoparticle size distribution enhances the amount of antibodies immobilized on the transducer material and the performance during the detection of the PSA. Significant results were obtained for the quantification of PSA, with a limit of detection of 1 ng·ml-1 and sensitivities of 0.085 and 0.056 µA·mL·ng-1 for the two transducer materials in only 5 min of detection.