Direct In Vivo Electrochemical Detection of Haemoglobin in Red Blood Cells

The electrochemical behavior of iron ion in haemoglobin provides insight to the chemical activity in the red blood cell which is important in the field of hematology. Herein, the detection of haemoglobin in human red blood cells on glassy carbon electrode (GC) was demonstrated. Red blood cells or raw blood cells was immobilized on a glassy carbon electrode surface with Nafion films employed to sandwich the layer of biological sample firmly on the electrode surface. Cyclic voltammetry (CV) analyses revealed a well-defined reduction peak for haemoglobin at about −0.30 V (vs. Ag/AgCl) at the red blood cell (GC-Nf-RBC-3Nf) and blood (GC-Nf-B-3Nf) film modified GCE in a pH 3.5 phosphate buffer solution. We further demonstrated that the complex biological conditions of a human red blood cell displayed no interference with the detection of haemoglobin. Such findings shall have an implication on the possibilities of studying the electrochemical behaviour of haemoglobin directly from human blood, for various scientific and clinical purposes.Singapore-MIT Alliance for Research and Technolog

Definitive evidence for fast electron transfer at pristine basal plane graphite from high-resolution electrochemical imaging

After all, it's active: High-resolution scanning electrochemical cell microscopy (SECCM) demonstrates that electron transfer at the basal plane of highly oriented pyrolytic graphite (HOPG) is fast. This finding requires radical revision of the current textbook model for HOPG electrochemistry

Electrochemistry at carbon nanotube forests : sidewalls and closed ends allow fast electron transfer

The electrochemical properties of the closed ends and sidewalls of pristine carbon nanotube forests are investigated directly using a nanopipet electrochemical cell. Both are shown to promote fast electron transfer, without any activation or processing of the carbon nanotube material required, in contrast to the current model in the literature

Group-IV graphene- and graphane-like nanosheets

We performed a first principles investigation on the structural and electronic properties of group-IV (C, SiC, Si, Ge, and Sn) graphene-like sheets in flat and buckled configurations and the respective hydrogenated or fluorinated graphane-like ones. The analysis on the energetics, associated with the formation of those structures, showed that fluorinated graphane-like sheets are very stable, and should be easily synthesized in laboratory. We also studied the changes on the properties of the graphene-like sheets, as result of hydrogenation or fluorination. The interatomic distances in those graphane-like sheets are consistent with the respective crystalline ones, a property that may facilitate integration of those sheets within three-dimensional nanodevices

Evidence of silicene in honeycomb structures of silicon on Ag(111)

In the search for evidence of silicene, a two-dimensional honeycomb lattice of silicon, it is important to obtain a complete picture for the evolution of Si structures on Ag(111), which is believed to be the most suitable substrate for growth of silicene so far. In this work we report the finding and evolution of several monolayer superstructures of silicon on Ag(111) depending on the coverage and temperature. Combined with first-principles calculations, the detailed structures of these phases have been illuminated. These structure were found to share common building blocks of silicon rings, and they evolve from a fragment of silicene to a complete monolayer silicene and multilayer silicene. Our results elucidate how silicene formes on Ag(111) surface and provide methods to synthesize high-quality and large-scale silicene.Comment: 6 pages, 4 figure

A new view of electrochemistry at highly oriented pyrolytic graphite

Major new insights on electrochemical processes at graphite electrodes are reported, following extensive investigations of two of the most studied redox couples, Fe(CN)64–/3– and Ru(NH3)63+/2+. Experiments have been carried out on five different grades of highly oriented pyrolytic graphite (HOPG) that vary in step-edge height and surface coverage. Significantly, the same electrochemical characteristic is observed on all surfaces, independent of surface quality: initial cyclic voltammetry (CV) is close to reversible on freshly cleaved surfaces (>400 measurements for Fe(CN)64–/3– and >100 for Ru(NH3)63+/2+), in marked contrast to previous studies that have found very slow electron transfer (ET) kinetics, with an interpretation that ET only occurs at step edges. Significantly, high spatial resolution electrochemical imaging with scanning electrochemical cell microscopy, on the highest quality mechanically cleaved HOPG, demonstrates definitively that the pristine basal surface supports fast ET, and that ET is not confined to step edges. However, the history of the HOPG surface strongly influences the electrochemical behavior. Thus, Fe(CN)64–/3– shows markedly diminished ET kinetics with either extended exposure of the HOPG surface to the ambient environment or repeated CV measurements. In situ atomic force microscopy (AFM) reveals that the deterioration in apparent ET kinetics is coupled with the deposition of material on the HOPG electrode, while conducting-AFM highlights that, after cleaving, the local surface conductivity of HOPG deteriorates significantly with time. These observations and new insights are not only important for graphite, but have significant implications for electrochemistry at related carbon materials such as graphene and carbon nanotubes

Electrospun Carbon Nanofiber Webs with Controlled Density of States for Sensor Applications

Electrospun carbon nanofiber (CNF) webs with controlled density of states (DOS) are synthesized through varying the carbonization conditions to manipulate the concentration of nanosized graphite domains. These materials exhibit adjustable electrochemical activity and biosensitivity: both electron transfer kinetics for various redox systems and direct electron transfer efficiencies with enzymes increase with the DOS of the CNF webs.United States. Dept. of Energ

Effect of Nitric Acid “Washing” Procedure on Electrochemical Behavior of Carbon Nanotubes and Glassy Carbon μ-Particles

The electroanalytic performances of glassy carbon paste electrode (GCPE), multi-walled carbon nanotube (MWCNT)-GCPE and double-walled carbon nanotube (DWCNT)-GCPE, which include HNO3 washed/unwashed materials, were compared by monitoring cyclic voltammograms of potassium ferricyanide and catechol. Electrodes were prepared by introducing proper amount of DWCNT and MWCNT into GCPE. First untreated materials (DWCNT, MWCNT, GC μ-particles) were used in the electrodes and then HNO3-treated materials were utilized for comparing difference in electrochemical performances. The effect of treatment procedure was also examined by applying Raman spectroscopy to treated and untreated materials. Moreover, TEM images were obtained for further investigation of MWCNT and DWCNT

Electrochemical oxidation of dihydronicotinamide adenine dinucleotide (NADH) : Comparison of highly oriented pyrolytic graphite (HOPG) and polycrystalline boron-doped diamond (pBDD) electrodes

The electro-oxidation of nicotinamide adenine dinucleotide (NADH) is studied at bare surfaces of highly oriented pyrolytic graphite (HOPG) and semi-metallic polycrystalline boron-doped diamond (pBDD). A comparison of these two carbon electrode materials is interesting because they possess broadly similar densities of electronic states that are much lower than most metal electrodes, but graphite has carbon sp2-hybridization, while in diamond the carbon is sp3-hybridised, with resulting major differences in bulk structure and surface termination. Using cyclic voltammetry (CV), it is shown that NADH oxidation is facile at HOPG surfaces but the reaction products tend to strongly adsorb, which causes rapid deactivation of the electrode activity. This is an important factor that needs to be taken into account when assessing HOPG and its intrinsic activity. It is also shown that NADH itself adsorbs at HOPG, a fact that has not been recognized previously, but has implications for understanding the mechanism of the electro-oxidation process. Although pBDD was found to be less susceptible to surface fouling, pBDD is not immune to deterioration of the electrode response, and the reaction showed more sluggish kinetics on this electrode. Scanning electrochemical cell microscopy (SECCM) highlights a significant voltammetric variation in electroactivity between different crystal surface facets that are presented to solution with a pBDD electrode. The electroactivity of different grains correlates with the local dopant level, as visualized by field emission-scanning electron microscopy. SECCM measurements further prove that the basal plane of HOPG has high activity towards NADH electro-oxidation. These new insights on NADH voltammetry are useful for the design of optimal carbon-based electrodes for NADH electroanalysis