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). The flow cells, have a channel (duct) geometry, with cell height of 25 μm, and are shown to be hydrodynamically well-defined, with laminar Poiseuille flow. In the arrangement where solution continuously flows over the electrode but the electrode is only exposed to the analyte for short periods of time, the SWNT electrodes do not foul and can be used repeatedly for many months. The LOD for dopamine (DA), reported herein, is significantly lower than previous reports using FIA-electrochemical detection. Furthermore, the SWNT electrodes can be used as grown, i.e., they do not require chemical modification or cleanup. The extremely low background signals of the SWNT electrodes, as a consequence of the sparse surface coverage and the low intrinsic capacitance of the SWNTs, means that no signal processing is required to measure the low currents for DA oxidation at trace levels. DA detection in artificial cerebral fluid is also possible with a LOD of ∼50 pM in 50 μL (∼2.5 fmol).

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. Using a galvanostatic approach, it was demonstrated the pH locally could be modified by over five pH units, depending on the initial pH of the mobile phase and the applied current. Electrochemical detection limits of 13.6 ppb sulfide were achieved using flow injection amperometry. This approach which offers local control of the pH of the detector electrode in a solution, which is far from ideal for optimized detection of the analyte of interest, enhances the capabilities of online electrochemical detection systems.

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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. A pH sensitive iridium oxide electrode electrodeposited on the disk electrode demonstrated that applied positive currents on the BDD ring, up to +50 μA, resulted in a local pH decrease of over 4 orders of magnitude, which remained stable over the measurement time of 600 s. pH generation experiments were found to be in close agreement with finite element simulations. The dual electrode arrangement was used to significantly improve the stripping peak signature for Hg in close to neutral conditions by the generation of pH = 2.0, locally. With the ability to create a localized pH change electrochemically in the vicinity of the detector electrode, this system could provide a simple method for optimized analysis at the source, e.g., river and sea waters.