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A highly redox active human whole blood-carbon nanomaterial modified electrode has been developed, which showed a redox peak (vs. Ag/AgCl) similar to that of hemoglobin (vs. Ag/AgCl) in red blood cells. Clinical relevance of this for direct electrochemical analysis of blood hemoglobin content (anemia) and thalassemia disease diagnosis was demonstrated.

The sulfide ion and its associated species (H2S and HS−) are widely referred to as toxic chemicals. However, at concentrations of ∼10–100 μM, it serves as a neurotransmitter and signaling agent in biological systems. Abnormalities in blood serum sulfide can be an indication of several diseases, including diabetes, wherein there is a significant reduction in the sulfide ion concentration (

Direct sensing of uric acid (UA) in an undiluted whole blood sample is reported here taking human whole blood as an analyte and a self-supporting electrolyte. Among various solid electrodes (Pt, Au, GCE, and GCE/Nafion) and carbon nanomaterials (carbon nanofibers, graphene oxide, graphite nanopowder, graphitized mesoporous carbon (GMC), single-walled carbon nanotubes, and multiwalled carbon nanotubes) tested, a GMC-modified glassy carbon electrode, designated as GCE/GMC, showed a remarkable response towards direct electrochemical oxidation of blood uric acid at ∼0.25 V vs. Ag/AgCl, unlike the poor and/or feeble current signals with the other unmodified and modified electrodes. It is plausible that the mesoporous nature of the GMC favours the formation of a blood-GMC bio-corona through internalization and provides straight access to blood-matrixed uric acid. Furthermore, the effects of the scan rate and interference with various biochemicals on the GCE/GMC were analysed. The electrochemical oxidation reaction is found to be diffusion controlled in nature and there is no interference from common biochemicals like ascorbic acid, glucose, tryptophan, H2O2, xanthine, hypoxanthine, cysteine, nitrate, nitrite, and sulfide in blood. Real blood UA sample analysis was demonstrated with comparable UA analysis results from the clinical measurement.

Electrocatalytic oxidative cyclization of dithiothreitol (DTT(SH)2) to a disulfide product was demonstrated on a Nafion/lead-ruthenium oxide pyrochlore chemically modified electrode (NPyCME). The process at the NPyCME with DTT(SH)2 is similar to the behaviour of protein in a disulfide linkage, which can be demonstrated by product analysis using HPLC coupled with UV spectroscopy. A possible electrocatalytic mechanism for DTT(SH)2 oxidation to dihydroxydithiane [i.e. cyclized DTT(S-S)] on the NPyCME was proposed in terms of Py-Ru(IV)/Py-Ru(VI) redox active sites. This physical aspect was further utilized for high precision analytical assays using flow injection analysis (FIA), with a linearity up to 50 microM and a detection limit (S/N = 3) of 28 nM (8.64 pg) in a 20 microL sample loop. This is the most sensitive method ever reported for DTT(SH)2 detection assays. The interference from dissolved oxygen, disulfide and glucose is almost negligible. The present method offers an easy route for extension to redox-related protein studies.

A disposable copper-plated screen-printed carbon electrode (CuSPE) was developed for the determination of hydrogen peroxide by flow injection analysis (FIA) at ambient temperature without deoxygenation. Cyclic voltammetry on the CuSPE in pH 7.4 phosphate buffer solution showed the growth of CuO and Cu2O. A well-defined reduction signal corresponding to the mediation of CuO and Cu2O occurred in the presence of hydrogen peroxide. The mechanistic study revealed that the reduction is a coupled-chemical reaction mechanism with the operation of pseudo-first order kinetics with respect to the concentration of Cu2O. The calculated electrochemical rate constant (ke) from Laviron’s model is 13.7 s−1. Systematic investigations were made to optimize the experimental parameters for hydrogen peroxide detection by FIA. With a poised potential of −0.3 V versus Ag/AgCl and a flow rate of 2 ml min−1, the calibration curve was found to be linear up to 200 μM hydrogen peroxide with a detection limit of 0.97 μM (S/N = 3). The CuSPE is fairly stable for repetitive measurements.

An electrochemically oxidized glassy carbon electrode was found to work excellently in the trace determination of Pb(II) using square-wave anodic stripping voltammetry. The associated phenomena were unravelled using chronocoulometry, linear scan voltammetry and electrochemical impedance spectroscopy. The chronocoulometry results showed that the double layer charge enormously increased on preanodization due to the creation of phenolic and quinolic oxide functional groups on the surface. The ac impedance analysis indicated that the duplex-layer model could illustrate the oxidized glassy carbon electrode behaviour quantitatively. The experimental factors, including preanodization condition, square-wave parameter, supporting electrolyte and pH, were optimized. Using the optimum parameters, the calibration curve was constructed and the detection limit was found to be 0.7 ppb (S/N = 3). The electrode is quite stable for repetitive measurements. The practical application was demonstrated to estimate trace Pb(II) in groundwater with very good precision.

A disposable copper nanoparticle-plated screen-printed carbon electrode (designated as Cun-SPE(100-nm)) provides a new material for the determination of native amino acids. All 20 underivatized amino acids can be sensitively determined at 0.0 V vs. Ag/AgCl in pH 8 phosphate buffer solution. The precisely controlled copper nanoparticles can boost up the CuIIO/CuI2O redox signal on the working surface without any prior pretreatment procedure. The formation of a reversible 1:1 CuIIO-amino acid complex on the Cun-SPE(100-nm) was proposed to play a key role in the reaction mechanism. Stable detection responses were obtained for all amino acids by flow injection analysis with detection limits (S/N = 3) that lie in the range of 24 nM-2.7 microM. Selected amino acids from six representative chemical natures were separated by HPLC and detected at the Cun-SPE(100-nm) with promising results.

Unusual electropolymerization of aniline to polyaniline (PANI) in a neutral pH solution has been successfully demonstrated using a multiwalled carbon nanotube (MWCNT) modified gold electrode (Au-MWCNT@PANIpH7). The modified electrode showed highly redox active surface confined peaks corresponding to the molecular transitions of leucoemeraldine-emeraldine and emeraldine-pernigraniline in pH 7 phosphate buffered solution (PBS), along with a low capacitance behavior, in contrast to the conventional acidic solution PANI systems. Control experiments in the absence of MWCNTs (i.e., Au/PANIpH7) and in an acidic medium, pH 2 (i.e., Au-MWCNT@PANIpH2), resulted in nil and poor redox features respectively. The physicochemical characterization of the MWCNT@PANIpH7 film by TEM, Raman spectroscopy, FTIR and UV-Vis revealed the presence of polaron type PANI structures on the MWCNT surface. More interestingly, MWCNT@PANIpH7 showed a highly selective electrocatalytic signal to ascorbic acid (AA) at a low oxidation potential, -15 mV vs. Ag/AgCl, without interference from nitrite, uric acid, dopamine, glucose, cysteine and citric acid in pH 7 PBS. Extended flow injection analysis yielded an excellent AA sensing response with a detection limit (signal-to-noise ratio = 3) of 42 nM, which is better than that of the conventional acid assisted MWCNT@PANIpH2 and MWCNT systems.