Manipulation and measurement of pH sensitive metal-ligand binding using electrochemical proton generation and metal detection.

Generator-detector electrodes can be used to both perturb and monitor pH dependant metal-ligand binding equilibria, in situ. In particular, protons generated at the generator locally influence the speciation of metal (Cu(2+)) in the presence of ligand (triethylenetetraamine), with the detector employed to monitor, in real time, free metal (Cu(2+)) concentrations.

Electrochemical flow injection analysis of hydrazine in an excess of an active pharmaceutical ingredient: achieving pharmaceutical detection limits electrochemically.

The quantification of genotoxic impurities (GIs) such as hydrazine (HZ) is of critical importance in the pharmaceutical industry in order to uphold drug safety. HZ is a particularly intractable GI and its detection represents a significant technical challenge. Here, we present, for the first time, the use of electrochemical analysis to achieve the required detection limits by the pharmaceutical industry for the detection of HZ in the presence of a large excess of a common active pharmaceutical ingredient (API), acetaminophen (ACM) which itself is redox active, typical of many APIs.

Laser heated boron doped diamond electrodes: effect of temperature on outer sphere electron transfer processes.

Thermoelectrochemical experiments can reveal significant information about electrochemical processes compared to ambient only measurements. Typical thermoelectrochemistry is performed using resistively heated wires or laser heated electrodes, both of which can suffer drawbacks associated with the electrode material employed. Boron doped diamond (BDD) is ideal for thermoelectrochemical investigations due to its extremely high thermal conductivity and diffusivity, extreme resistance to thermal ablation (can withstand laser power densities, Pd, of GW cm(-2) for nanosecond pulses) and excellent electrochemical properties (low background currents and wide potential window).

In situ optimization of pH for parts-per-billion electrochemical detection of dissolved hydrogen sulfide using boron doped diamond flow electrodes.

A novel electrochemical approach to the direct detection of hydrogen sulfide (H2S), in aqueous solutions, covering a wide pH range (acid to alkali), is described. In brief, a dual band electrode device is employed, in a hydrodynamic flow cell, where the upstream electrode is used to controllably generate hydroxide ions (OH(-)), which flood the downstream detector electrode and provide the correct pH environment for complete conversion of H2S to the electrochemically detectable, sulfide (HS(-)) ion. All-diamond, coplanar conducting diamond band electrodes, insulated in diamond, were used due to their exceptional stability and robustness when applying extreme potentials, essential attributes for both local OH(-) generation via the reduction of water, and for in situ cleaning of the electrode, post oxidation of sulfide.

Fabrication route for the production of coplanar, diamond insulated, boron doped diamond macro- and microelectrodes of any geometry.

Highly doped, boron doped diamond (BDD) is an electrode material with great potential, but the fabrication of suitable electrodes in a variety of different geometries both at the macro- and microscale, with an insulating material that does not compromise the material properties of the BDD, presents technical challenges. In this Technical Note, a novel solution to this problem is presented, resulting in the fabrication of coplanar macro- and microscale BDD electrodes, insulated by insulating diamond, at the single and multiple, individually addressable level. Using a laser micromachining approach, the required electrode(s) geometry is machined into an insulating diamond substrate, followed by overgrowth of high quality polycrystalline BDD (pBDD) and polishing to reveal approximately nanometer roughness, coplanar all-diamond structures.

In situ control of local pH using a boron doped diamond ring disk electrode: optimizing heavy metal (mercury) detection.

A novel electrochemical approach to modifying aqueous solution pH in the vicinity of a detector electrode in order to optimize the electrochemical measurement signal is described. A ring disk electrode was employed where electrochemical decomposition of water on the ring was used to generate a flux of protons which adjusts the local pH controllably and quantifiably at the disk. Boron doped diamond (BDD) functioned as the electrode material given the stability of this electrode surface especially when applying high potentials (to electrolyze water) for significant periods of time.

Ultrasensitive detection of dopamine using a carbon nanotube network microfluidic flow electrode.

The electrochemical measurement of dopamine (DA), in phosphate buffer solution (pH 7.4), with a limit of detection (LOD) of ∼5 pM in 50 μL (∼ 250 attomol) is achieved using a band electrode comprised of a sparse network of pristine single-walled carbon nanotubes (SWNTs), which covers <1% of the insulating substrate. The SWNT electrodes are deployed as amperometric (anodic) detectors in microfluidic cells, produced by microstereolithography, designed specifically for flow injection analysis (FIA).

Dissolution kinetics of polycrystalline calcium sulfate-based materials: influence of chemical modification.

Using a channel flow cell (CFC) system, the dissolution kinetics of polycrystalline gypsum-based materials have been examined with the aim of understanding their interaction with water, a property that limits the applications of the material in many situations. ICP (inductively coupled plasma) analysis of elemental concentrations in solution as a function of time yields surface fluxes by using a finite element modeling approach to simulate the hydrodynamic behavior within the CFC. After correction for surface roughness, a value for the intrinsic dissolution flux into water of pure polycrystalline gypsum, CaSO(4).