Attributes of direct current aperiodic and alternating current harmonic components derived from large amplitude Fourier transformed voltammetry under microfluidic control in a channel electrode.

The flow rate dependencies of the aperiodic direct current (dc) and fundamental to eighth alternating current (ac) harmonic components derived from large-amplitude Fourier transformed ac (FT-ac) voltammetry have been evaluated in a microfluidic flow cell containing a 25 µm gold microband electrode. For the oxidation of ferrocenemethanol ([FcMeOH]/[FcMeOH](+) process) in aqueous 0.1 M KNO(3) electrolyte, standard "Levich-like" dc behavior is observed for the aperiodic dc component, which enables the diffusion coefficient for FcMeOH to be obtained. In experimental studies, the first and second ac harmonic components contain contributions from the double layer capacitance current, thereby allowing details of the non-Faradaic current to be established. In contrast, the higher order harmonics and dc aperiodic component are essentially devoid of double layer capacitance contributions allowing the faradaic current dependence on flow rate to be studied. Significantly, flow rate independent data conforming to linear diffusion controlled theory are found in the sixth and higher ac harmonics at a frequency of 15 Hz and for all ac harmonics at a frequency of ≥ 90 Hz. Analysis of FT-ac voltammograms by theory based on stationary microband or planar electrode configurations confirms that stationary microband and planar electrode configurations and experimental data all converge for the higher order harmonics and establishes that the electrode kinetics are very fast (≥1 cms(-1)). The ability to locate, from a single experiment, a dc Faradaic component displaying Levich behavior, fundamental and second harmonics that contain details of the double layer capacitance, and Faradaic ac higher order harmonic currents that are devoid of capacitance, independent of the volume flow rate and also conform closely to mass transport by planar diffusion, provides enhanced flexibility in mass transport and electrode kinetic analysis and in understanding the performance of hydrodynamic electrochemical cells and reactors.

A method for the positioning and tracking of small moving particles.

On the move: Electrochemistry has been used to detect and monitor the motion of a single 330 microm sphere in both time and space (see picture). The motion was recorded simultaneously by video and chronoamperometry, which showed an excellent correlation. The ability to fabricate electrode arrays capable of spatial resolution at the sub-micrometer scale opens the possibility of using this technique to monitor considerably smaller particles.

The electrochemical detection of droplets in microfluidic devices.

This paper presents a new electrochemical method for the detection and characterisation of aqueous droplets in an organic carrier fluid (1,2-dichloroethane) formed in flow-focusing microfluidic devices. The devices consist of a conventional flow-focusing channel 250 microm wide and 250 microm deep cast out of poly(dimethylsiloxane) (PDMS) which is sealed onto a glass substrate containing a set of microelectrodes 100 microm long. Chronoamperometric analysis of a suitable electrolyte contained in the organic phase is presented for characterising the droplet frequency and size. This chronoamperometric method is then extended to a dual working electrode approach in order to determine the velocity of the droplet. Good agreement between experimental measurements and theory was observed.

Study of miscible and immiscible flows in a microchannel using magnetic resonance imaging.

Magnetic resonance imaging (MRI) is a noninvasive technique that can be used to visualize mixing processes in optically opaque systems in up to three dimensions. Here, MRI has been used for the first time to obtain both cross-sectional velocity and concentration maps of flow through an optically opaque Y-shaped microfluidic sensor. Images of 23 micromx23 microm resolution were obtained for a channel of rectangular cross section (250 micromx500 microm) fed by two square inlets (250 micromx250 microm). Both miscible and immiscible liquid systems have been studied. These include a system in which the coupling of flow and mass transfer has been observed, as the diffusion of the analyte perturbs local hydrodynamics. MRI has been shown to be a versatile tool for the study of mixing processes in a microfluidic system via the multidimensional spatial resolution of flow and mass transfer.

Quantitative kinetic analysis in a microfluidic device using frequency-domain fluorescence lifetime imaging.

A novel microfluidic approach for the quantification of reaction kinetics is presented. A three-dimensional finite difference numerical simulation was developed in order to extract quantitative kinetic information from fluorescence lifetime imaging experimental data. This approach was first utilized for the study of a fluorescence quenching reaction within a microchannel; the lifetime of a fluorophore was used to map the diffusion of a quencher across the microchannel. The approach was then applied to a more complex chemical reaction between a fluorescent amine and an acid chloride, via numerical simulation the bimolecular rate constant for this reaction was obtained.

Microfluidic channel flow cell for simultaneous cryoelectrochemical electron spin resonance.

A novel microfluidic electrochemical channel flow cell has been constructed for in situ operation in a cylindrical TE011 resonant ESR cavity under variable temperature conditions. The cell has a U-tube configuration, consisting of an inlet and outlet channel which run parallel and contain evaporated gold film working, pseudo-reference, and counter electrodes. This geometry was employed to permit use in conjunction with variable temperature apparatus which does not allow a flow-through approach. The cell is characterized qualitatively and quantitatively using the one-electron reduction of p-bromonitrobenzene in acetonitrile at room temperature as a model system, and the ESR signal-flow rate response is validated by use of three-dimensional digital simulation of the concentration profile for a stable electrogenerated radical species under hydrodynamic conditions. The cell is then used to obtain ESR spectra for a number of radical species in acetonitrile at 233 K, including the radical anions of m- and p-iodonitrobenzene, o-bromonitrobenzene, and m-nitrobenzyl chloride, the latter three being unstable at room temperature. Spectra are also presented for the radical anion of 2-chloranthraquinone and the crystal violet radical, which display improved resolution at low temperatures.

A microfluidic channel flow cell for electrochemical ESR.

The design, fabrication, and characterization of microfluidic channel flow devices for in situ simultaneous hydrodynamic electrochemical ESR is reported. The microelectrochemical reactors consist of gold film electrodes situated within rectangular ducts of height 350 microm and widths in the range 500-2000 microm. The small dimensions of the channels result in minimal dielectric loss when centralized within a cylindrical TE011 resonant cavity, leading to a high level of sensitivity. This is demonstrated by using the one-electron oxidation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in acetonitrile as a model system, wherein the ESR spectra obtained for the corresponding stable radical cation are of a high signal-to-noise ratio. Signal intensity is measured as a function of flow rate for this system, and the behavior is validated by means of 3-dimensional numerical modeling of the hydrodynamic flow profile.

The effect of cruciferous and leguminous sprouts on genotoxicity, in vitro and in vivo.

Vegetable consumption is associated with a reduced risk of colorectal cancer, which is the second most common cancer after lung/breast cancer within Europe. Some putative protective phytochemicals are found in higher amounts in young sprouts than in mature plants. The effect of an extract of mixed cruciferous and legume sprouts on DNA damage induced by H(2)O(2) was measured in HT29 cells using single cell microgelelectrophoresis (comet). Significant antigenotoxic effect (P < or = 0.05) was observed when HT29 cells were pre-incubated with the extract (100 and 200 microL/mL) for 24 hours and then challenged with H(2)O(2). A parallel design intervention study was carried out on 10 male and 10 female healthy adult volunteers (mean age = 25.5 years) fed 113 g of cruciferous and legume sprouts daily for 14 days. The effect of the supplementation was measured on a range of parameters, including DNA damage in lymphocytes (comet), the activity of various detoxifying enzymes (glutathione S-transferase, glutathione peroxidase, and superoxide dismutase), antioxidant status using the ferric reducing ability of plasma assay, plasma antioxidants (uric acid, ascorbic acid, and alpha-tocopherol), blood lipids, plasma levels of lutein, and lycopene. A significant antigenotoxic effect against H(2)O(2)-induced DNA damage was shown in peripheral blood lymphocytes of volunteers who consumed the supplemented diet when compared with the control diet (P = 0.04). No significant induction of detoxifying enzymes was observed during the study, neither were plasma antioxidant levels or activity altered. The results support the theory that consumption of cruciferous vegetables is linked to a reduced risk of cancer via decreased damage to DNA.