The Determination of Methanol Using an Electrolytically Fabricated Nickel Microparticle Modified Boron Doped Diamond Electrode

A nickel modified boron doped diamond (Ni-BDD) electrode and nickel foil electrode were used in the determination of methanol in alkaline solutions. The Ni-BDD electrode was electrodeposited from a 1 mM Ni(NO(3))(2) solution (pH 5), followed by repeat cycling in KOH. Subsequent analysis utilised the Ni(OH)(2)/NiOOH redox couple to electrocatalyse the oxidation of methanol. Methanol was determined to limits of 0.3 mM with a sensitivity of 110 nA/mM at the Ni-BDD electrode. The foil electrode was less sensitive achieving a limit of 1.6 mM and sensitivity of 27 nA/mM. SEM analysis of the electrodes found the Ni-BDD to be modified by a quasi-random microparticle array.

Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM

We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.

Raman microscopic analysis of internal stress in boron-doped diamond

Analysis of the induced stress on undoped and boron-doped diamond (BDD) thin films by confocal Raman microscopy is performed in this study to investigate its correlation with sample chemical composition and the substrate used during fabrication. Knowledge of this nature is very important to the issue of long-term stability of BDD coated neurosurgical electrodes that will be used in fast-scan cyclic voltammetry, as potential occurrence of film delaminations and dislocations during their surgical implantation can have unwanted consequences for the reliability of BDD-based biosensing electrodes. To achieve a more uniform deposition of the films on cylindrically-shaped tungsten rods, substrate rotation was employed in a custom-built chemical vapor deposition reactor. In addition to visibly preferential boron incorporation into the diamond lattice and columnar growth, the results also reveal a direct correlation between regions of pure diamond and enhanced stress. Definite stress release throughout entire film thicknesses was found in the OPEN ACCESS current Raman mapping images for higher amounts of boron addition. There is also a possible contribution to the high values of compressive stress from sp2 type carbon impurities, besides that of the expected lattice mismatch between film and substrate.

Simultaneous Differential Pulse Voltammetric Determination of Ascorbic Acid and Caffeine in Pharmaceutical Formulations Using a Boron-Doped Diamond Electrode

A cathodically pretreated boron-doped diamond electrode was used for the simultaneous anodic determination of ascorbic acid (AA) and caffeine (CAF) by differential pulse voltammetry Linear calibration curves (r = 0 999) were obtained from 1 9 x 10(-5) to 2 I x 10(-4) mol L(-1) for AA and from 9 7 x 10(-6) to 1 1 x 10-4 mol L(-1) for CAF. with detection limits of 19 wool L(-1) and 7 0 mu nol L(-1). respectively This method was successfully applied for the determination of AA and CAF in pharmaceutical formulations. with results equal to those obtained using a HPLC reference method

Simultaneous voltammetric determination of paracetamol and caffeine in pharmaceutical formulations using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential Pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials Of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 x 10(-7) mol L(-1) to 8.3 x 10(-7) mol L(-1) for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 x 10(-7) mol L-1 and 3.5 x 10(-8) mol L(-1), respectively. The proposed method Was Successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level). (C) 2008 Elsevier BY. All rights reserved.

The Fabrication and Characterization of a Nickel Nanoparticle Modified Boron Doped Diamond Electrode for Electrocatalysis of Primary Alcohol Oxidation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Interaction of Organophosphorus Pesticides with DNA Nucleotides on a Boron-Doped Diamond Electrode

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Transport properties of polycrystalline boron doped diamond

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Multiple conduction paths in boron δ-doped diamond structures

Impedance spectroscopy has been used to investigate conductivity within boron-doped diamond in an intrinsic/delta-doped/intrinsic (i-d-i) multilayer structure. For a 5 nm thick delta layer, three conduction pathways are observed, which can be assigned to transport within the delta layer and to two differing conduction paths in the i-layers adjoining the delta layer. For transport in the i-layers, thermal trapping/detrapping processes can be observed, and only at the highest temperature investigated (673 K) can transport due to a single conduction process be seen. Impedance spectroscopy is an ideal nondestructive tool for investigating the electrical characteristics of complex diamond structures.

Electronic properties of homoepitaxial (111) highly boron-doped diamond films

The use of diamond as a semiconductor for the realization of transistor structures, which can operate at high temperatures (>700 K), is of increasing interest. In terms of bipolar devices, the growth of n-type phosphorus doped diamond is more efficient on the (111) growth plane; p-type boron-doped diamond growth has been most usually grown in the (100) direction and, hence, this study into the electronic properties, at high temperatures, of boron-doped diamond (111) homoepitaxial layers. It is shown that highly doped layers (hole carrier concentrations as high as 2×1020 cm-3) can be produced without promoting the onset of (unwanted) hopping conduction. The persistence of valance-band conduction in these films enables relatively high mobility values to be measured ( ~ 20 cm2/V?s) and, intriguingly, these values are not significantly reduced at high temperatures. The layers also display very low compensation levels, a fact that may explain the high mobility values since compensation is required for hopping conduction. The results are discussed in terms of the potential of these types of layers for use with high temperature compatible diamond transistors.

Electron field emission from boron doped microcrystalline diamond

Field emission properties of hot filament chemical vapor deposited boron doped polycrystalline diamond have been studied. Doping level (N-B) of different samples has been varied by the B/C concentration in the gas feed during the growth process and doping saturation has been observed for high B/C ratios. Threshold field (E-th) for electron emission as function of B/C concentration has been measured, and the influences of grain boundaries, doping level and surface morphology on field emission properties have been investigated. Carrier transport through conductive grains and local emission properties of surface sites have been figured out to be two independent limiting effects in respect of field emission. Emitter current densities of 500 nA cm(-2) were obtained using electric fields less than 8 V/mu m. (c) 2007 Elsevier B.V. All rights reserved.

Determination of Total Nitrosamines in Vegetables Cultivated Organic and Conventional Using Diamond Electrode

Vegetables were analyzed for total N-nitrosamines (NAs) and the influence of disinfection processes was assessed. Differences in NAs found in cabbage, spinach, and broccoli were determined by square wave voltammetry using a boron-doped diamond electrode. Analysis of samples showed that all samples contained detectable levels of NAs but the results indicated that organic contained less than conventionally grown products. The sum of the total NAs was higher in the cabbage samples, ranging between 2.8-3.1 ppb and lower in broccoli samples at 0.2-1.1 ppb. The method described is simple, rapid, selective, and sensitive. The results suggested that the disinfection process affects the level of NAs, in this manner affecting the level of human exposure to NAs. © 2012 Springer Science+Business Media New York.

Diamond-based electrode for chronic sensing in deep brain stimulation

This thesis describes the development of a sensing electrode and electronic research platform that enables the measurement of fluctuating levels of neurotransmitters in the human brain. Boron doped diamond electrodes were created via a custom developed chemical vapor deposition reactor for measurement of neurotransmitters using Fast Scan Cyclic Voltammetry.

Investigation of mediated oxidation of ascorbic acid by ferrocenemethanol using large-amplitude fourier transformed ac voltammetry under quasi-reversible electron-transfer conditions at an indium tin oxide electrode

The ability of the technique of large-amplitude Fourier transformed (FT) ac voltammetry to facilitate the quantitative evaluation of electrode processes involving electron transfer and catalytically coupled chemical reactions has been evaluated. Predictions derived on the basis of detailed simulations imply that the rate of electron transfer is crucial, as confirmed by studies on the ferrocenemethanol (FcMeOH)-mediated electrocatalytic oxidation of ascorbic acid. Thus, at glassy carbon, gold, and boron-doped diamond electrodes, the introduction of the coupled electrocatalytic reaction, while producing significantly enhanced dc currents, does not affect the ac harmonics. This outcome is as expected if the FcMeOH (0/+) process remains fully reversible in the presence of ascorbic acid. In contrast, the ac harmonic components available from FT-ac voltammetry are predicted to be highly sensitive to the homogeneous kinetics when an electrocatalytic reaction is coupled to a quasi-reversible electron-transfer process. The required quasi-reversible scenario is available at an indium tin oxide electrode. Consequently, reversible potential, heterogeneous charge-transfer rate constant, and charge-transfer coefficient values of 0.19 V vs Ag/AgCl, 0.006 cm s (-1) and 0.55, respectively, along with a second-order homogeneous chemical rate constant of 2500 M (-1) s (-1) for the rate-determining step in the catalytic reaction were determined by comparison of simulated responses and experimental voltammograms derived from the dc and first to fourth ac harmonic components generated at an indium tin oxide electrode. The theoretical concepts derived for large-amplitude FT ac voltammetry are believed to be applicable to a wide range of important solution-based mediated electrocatalytic reactions.

Electrochemistry of room temperature protic ionic liquids

Eighteen protic ionic liquids containing different combinations of cations and anions, hydrophobicity, viscosity, and conductivity have been synthesized and their physicochemical properties determined. In one series, the diethanolammonium cations were combined with acetate, formate, hydrogen sulfate, chloride, sulfamate, and mesylate anions. In the second series, acetate and formate anions were combined with amine bases, triethylamine, diethylamine, triethanolamine, di-n-propylamine, and di-n-butylamine. The electrochemical characteristics of the eight protic ionic liquids that are liquid at room temperature (RTPILs) have been determined using cyclic, microelectrode, and rotating disk electrode voltammetries. Potential windows of the RTPILs have been compared at glassy carbon, platinum, gold, and boron-doped diamond electrodes and generally found to be the largest in the case of glassy carbon. The voltammetry of IUPAC recommended potential scale reference systems, ferrocene/ferrocenium and cobaltocenium/cobaltocene, have been evaluated and found to be ideal in the case of the less viscous RTPILs but involve adsorption in the highly viscous ones. Other properties such as diffusion coefficients, ionic conductivity, and double layer capacitance also have been measured. The influence of water on the potential windows, viscosity, and diffusion has been studied systematically by deliberate addition of water to the dried ionic liquids. The survey highlights the problems with voltammetric studies in highly viscous room temperature protic ionic liquids and also suggests the way forward with respect to their possible industrial use.