A new type of flow platform for electrochemical and spectroelectrochemical measurements is presented. Finite element method simulations confirm that the hydrodynamic profile within the device is not turbulent and provides an analytical platform for the investigation of homogeneous kinetics, radical lifetimes, and reaction mechanisms. The modular "plug and play" configuration of the platform allows one to carry out electrochemistry and spectroscopy individually or simultaneously. Specific demonstrations of electroanalytical measurements using the flow system platform includes voltammetric analysis of organometallic compounds and quantitative analysis of ascorbic acid in commercial orange juice samples. Combined spectroelectrochemical demonstrations include electrochemical luminescence of ruthenium compounds and ligand exchange reactions of iron complexes using UV-vis spectroscopy.

We present herein localized galvanostatic and potentiodynamic measurements on lithium iron phosphate (LFP) particles, using the combination of a scanning micropipette contact method (SMCM) and scanning electron microscopy (SEM). The proposed technique allows small substrate areas (similar to 10 mu m in diameter) decorated with LFP particles to be probed within a lithium electrolyte solution in organic carbonate solvents (0.1 M LiClO4 in propylene carbonate in the present study). SEM images of the scanned area allow the correlation of each electrochemical response to the number, and volume of the probed particles. Under favorable conditions, single particles are found within the measurement areas, thus enabling the determination of single particle properties in an anaerobic environment without the additional complications arising from the presence of binders and electronically conductive fillers. The ability to analyze a material with complementary experimental techniques at the single particle level should create new opportunities for fundamental studies and for the quality control of granular materials. (C) 2016 Elsevier B.V. All rights reserved.

A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1 mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca2+ flux (jCa2+), is first order with respect to the interfacial proton concentration and given by the following rate law: jCa2+=k0[H+], with k0=0.099±0.008 cm s−1. Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10–20 nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient.

Dissolution kinetics of the (110) face of salicylic acid in aqueous solution is determined by hopping intermittent contact-scanning electrochemical microscopy (HIC-SECM) using a 2.5 μm diameter platinum ultramicroelectrode (UME). The method operates by translating the probe UME towards the surface at a series of positions across the crystal and inducing dissolution via the reduction of protons to hydrogen, which titrates the weak acid and promotes the dissolution reaction, but only when the UME is close to the crystal. Most importantly, as dissolution is only briefly and transiently induced at each location, the initial dissolution kinetics of an as-grown single crystal surface can be measured, rather than a surface which has undergone significant dissolution (pitting), as in other techniques. Mass transport and kinetics in the system are modelled using finite element method simulations which allows dissolution rate constants to be evaluated. It is found that the kinetics of an 'as-grown' crystal are much slower than for a surface that has undergone partial bulk dissolution (mimicking conventional techniques), which can be attributed to a dramatic change in surface morphology as identified by atomic force microscopy (AFM). The 'as-grown' (110) surface presents extended terrace structures to the solution which evidently dissolve slowly, whereas a partially dissolved surface has extensive etch features and step sites which greatly enhance dissolution kinetics. This means that crystals such as salicylic acid will show time-dependent dissolution kinetics (fluxes) that are strongly dependent on crystal history, and this needs to be taken into account to fully understand dissolution.

The successful development of scanning probe techniques to characterize corrosion in situ using multifunctional probes is intrinsically tied to surface topography signal decoupling from the measured electrochemical fluxes. One viable strategy is the shear force controlled scanning microcapillary method. Using this method, pulled quartz micropipettes with an aperture of 500 nm diameter were used to resolve small and large variations in topography in order to quantify the local corrosion rate of microgalvanically and galvanically corroded Mg alloys. To achieve topography monitoring of corroded surfaces, shear force feedback was employed to position the micropipette at a reproducible working height above the substrate. We present proof of concept measurements over a galvanic couple of a magnesium alloy (AE44) and mild steel along with a microgalvanically corroded ZEK100 Mg alloy, which illustrates the ability of shear force to track small (1.4 μm) and large (700 μm) topographic variations from high aspect ratio features. Furthermore, we demonstrate the robustness of the technique by acquiring topographic data for 4 mm along the magnesium-steel galvanic couple sample and a 250 × 30 μm topography map over the ZEK100 Mg alloy. All topography results were benchmarked using standard optical microscopies (profilometry and confocal laser scanning microscopy).

Maintaining a well-defined tip-to-substrate separation is a critical area of development in scanning electrochemical microscopy (SECM). One technique that provides topographic data independently to the electrochemical measurement is shear force (SF) SECM. SF measurements are highly sensitive to factors including the tip-to-substrate separation, experimental solution, and probe geometry. We present a procedure for the fabrication of highly reproducible electrochemical probes with an active electrode disc with radii between 3nm to 190nm. A systematic study of the SF characteristics of these nano electrodes provides details on how to achieve the highest sensitivity and stability of SF signals, and maximize the number of SF sensitive frequencies. A new methodology to identify SF sensitive frequencies without needing to immerse the probes in solution or approach the surface is presented. Furthermore, we demonstrate that the greatest source of error in achieving reproducible SF behavior lies in the positioning of the piezo electric components and the piezo-nano electrode interface.

A microscale vertical fluidic cell system has been implemented, based on a simple theta pipet pulled to a sharp point (ca. 10-20 pm diameter for the studies herein) and positioned with a high degree of control on a surface. The dual channel arrangement allows an electric field to be generated between an electrode in each compartment of the pipet that can be used to control the electromigration of charged species between the two compartments, across a thin liquid meniscus in contact with the substrate of interest. By visualizing the interfacial region using laser scanning confocal microscopy, the adsorption of fluorescently-labeled materials on surfaces is monitored quantitatively in real time, exemplified through studies of the adsorption of anionic microparticles (1.1 mu m diameter) on positively and negatively charged substrate surfaces of poly-L-lysine (PLL) and poly-L-glutamic acid (PGA), respectively, on glass. These studies highlight significant electrostatic effects on adsorption rates and also that the adsorption of these particles is dominated by the three phase meniscus/solid/air boundary. The technique is easily modified to the case of a submerged substrate, resulting in a much larger deposition area. Finite element method modeling is used to calculate local electric field strengths that are used to understand surface deposition patterns. To demonstrate the applicability of the technique to live biological substrates, the delivery of fluorescent particles directly to the surface of a single root hair cell of Zea mays is demonstrated. The mobile pipet allows deposition to be directed to specific regions of the cell, allowing discrete sites to be labeled with particles. Finally, the technique is used to study the uptake of fluorescent polymer molecules to single root hair cells, with quantitative analysis of the adsorption rates of vinyl-sulfonic acid copolymers, with varying rhodamine B content.

Objectives: To investigate the formation of hydroxyapatite (HAP) from calcium silicate and the deposition of calcium silicate onto sound and acid eroded enamel surfaces in order to investigate its repair and protective properties.Methods: Calcium silicate was mixed with phosphate buffer for seven days and the resulting solids analysed for crystalline phases by Raman spectroscopy. Deposition studies were conducted on bovine enamel surfaces. Acid etched regions were produced on the enamel surfaces using scanning electrochemical cell microscopy (SECCM) with acid filled pipettes and varying contact times. Following treatment with calcium silicate, the deposition was visualised with FE-SEM and etch pit volumes were measured by AFM. A second set of bovine enamel specimens were pre-treated with calcium silicate and fluoride, before acid exposure with the SECCM. The volumes of the resultant acid etched pits were measured using AFM and the intrinsic rate constant for calcium loss was calculated.Results: Raman spectroscopy confirmed that HAP was formed from calcium silicate. Deposition studies demonstrated greater delivery of calcium silicate to acid eroded than sound enamel and that the volume of acid etched enamel pits was significantly reduced following one treatment (p < 0.05). In the protection study, the intrinsic rate constant for calcium loss from enamel was 0.092 +/- 0.008 cm/s. This was significantly reduced, 0.056 +/- 0.005 cm/s, for the calcium silicate treatments (p < 0.0001).Conclusions: Calcium silicate can transform into HAP and can be deposited on acid eroded and sound enamel surfaces. Calcium silicate can provide significant protection of sound enamel from acid challenges. Clinical Significance: Calcium silicate is a material that has potential for a new approach to the repair of demineralised enamel and the protection of enamel from acid attacks, leading to significant dental hard tissue benefits. (C) 2014 Elsevier Ltd. All rights reserved.

A new approach to the study of ionic crystal dissolution kinetics is described, based on the use of a dual-barrel theta conductance micropipet. The solution in the pipet is undersaturated with respect to the crystal of interest, and when the meniscus at the end of the micropipet makes contact with a selected region of the crystal surface, dissolution occurs causing the solution composition to change. This is observed, with better than 1 ms time resolution, as a change in the ion conductance current, measured across a potential bias between an electrode in each barrel of the pipet. Key attributes of this new technique are: (i) dissolution can be targeted at a single crystal surface; (ii) multiple measurements can be made quickly and easily by moving the pipet to a new location on the surface; (iii) materials with a wide range of kinetics and solubilities are open to study because the duration of dissolution is controlled by the meniscus contact time; (iv) fast kinetics are readily amenable to study because of the intrinsically high mass transport rates within tapered micropipets; (v) the experimental geometry is well-defined, permitting finite element method modeling to allow quantitative analysis of experimental data. Herein, we study the dissolution of NaCl as an example system, with dissolution induced for just a few milliseconds, and estimate a first-order heterogeneous rate constant of 7.5 (±2.5) × 10(-5) cm s(-1) (equivalent surface dissolution flux ca. 0.5 μmol cm(-2) s(-1) into a completely undersaturated solution). Ionic crystals form a huge class of materials whose dissolution properties are of considerable interest, and we thus anticipate that this new localized microscale surface approach will have considerable applicability in the future.

A channel flow cell, fabricated using microsterolithography (MSL), has been employed to determine the rate constant for the homogenous oxidation of ascorbic acid (AA) by an electrogenerated oxidant in aqueous solution under physiological pH conditions using a dual gold microband electrode format. Specifically, the oxidation of ferrocenylmethyl trimethyl-ammonium (FcTMA(+)) at an upstream electrode produce FcTMA(2+), which oxidises AA in solution, yielding FcTMA(+) which can undergo further heterogeneous oxidation at the upstream electrode. In addition, by setting the downstream electrode potential to a value where FcTMA(2+) is detected at a transport-limited rate, collection efficiency measurements are also possible in a redox titration format. The benefits of studying homogeneous kinetics, and particularly this catalytic EC' process, in a flow through system using a dual electrode format are highlighted. Collection efficiency measurements are shown to be particularly attractive for the detection of low levels of AA and are much more sensitive than measurements at a single electrode, particularly as a range of device parameters, such as flow rate, electrode size and electrode separation can be tuned to optimise detection. Various electrode sizes operating in the generation/collection (GC) mode have been assessed, with the optimum geometry of those studied (for the highest collection efficiency in the absence of homogenous reactions) being a small upstream generator electrode (25 mu M long), a large downstream collector electrode (400 mu M long), separated by a few tens of microns, in a channel of 200 mu m height and 4 mm width. A full model for the cell hydrodynamics and mass transport has been developed using finite element modelling and extensive experiments are reported assessing the collection efficiency for different electrode geometries and AA concentrations. The homogeneous rate constant for the reaction between FcTMA(2+) and AA is 5.5 (+/- 1.6) x 10(5) M-1 s(-1). (c) 2013 Elsevier B.V. All rights reserved.

Scanning electrochemical cell microscopy (SECCM) is a new pipette-based imaging technique purposely designed to allow simultaneous electrochemical, conductance, and topographical visualization of surfaces and interfaces. SECCM uses a tiny meniscus or droplet, at the end of a double-barreled (theta) pipette, for high-resolution functional imaging and nanoscale electrochemical measurements. Here we introduce this technique and provide an overview of its principles, instrumentation, and theory. We discuss the power of SECCM in resolving complex structure-activity problems and provide considerable new information on electrode processes by referring to key example systems, including graphene, graphite, carbon nanotubes, nanoparticles, and conducting diamond. The many longstanding questions that SECCM has been able to answer during its short existence demonstrate its potential to become a major technique in electrochemistry and interfacial science.

The intrinsic electrochemical properties and activity of single walled carbon nanotube (SWNT) network electrodes modified by a drop-cast Nafion film have been determined using the one electron oxidation of ferrocene trimethyl ammonium (FcTMA(+)) as a model redox probe in the Nafion film. Facilitated by the very low transport coefficient of FcTMA(+) in Nafion (apparent diffusion coefficient of 1.8 × 10(-10) cm(2) s(-1)), SWNTs in the 2-D network behave as individual elements, at short (practical) times, each with their own characteristic diffusion, independent of neighbouring sites, and the response is diagnostic of the proportion of SWNTs active in the composite. Data are analysed using candidate models for cases where: (i) electron transfer events only occur at discrete sites along the sidewall (with a defect density typical of chemical vapour deposition SWNTs); (ii) all of the SWNTs in a network are active. The first case predicts currents that are much smaller than seen experimentally, indicating that significant portions of SWNTs are active in the SWNT-Nafion composite. However, the predictions for a fully active SWNT result in higher currents than seen experimentally, indicating that a fraction of SWNTs are not connected and/or that not all SWNTs are wetted completely by the Nafion film to provide full access of the redox mediator to the SWNT surface.

A wide variety of steric and electronic features can be incorporated into transition metal coordination complexes, offering the prospect of rationally-designed therapeutic agents with novel mechanisms of action. Here we compare the chemical reactivity and anticancer activity of organometallic Os-II complexes [Os(eta(6)-arene)(XY)Z]PF6 where arene = p-cymene or biphenyl, XY = N,N'-chelated phenyliminopyridine or phenylazopyridine derivatives, and Z = Cl or I. The X-ray crystal structure of [Os(eta(6)-p-cym)(Impy-OH)I]PF6 center dot 0.5CH(2)Cl(2)center dot H2O (Impy-OH = 4-[(2-pyridinylmethylene)amino]-phenol) is reported. Like the azopyridine complexes we reported recently (Dalton Trans., 2011, 40, 10553-10562), some iminopyridine complexes are also potently active towards cancer cells (nanomolar IC50 values). However we show that, unlike the azopyridine complexes, the iminopyridine complexes can undergo aquation, bind to the nucleobase guanine, and oxidize coenzyme nicotine adenine dinucleotide (NADH). We report the first detection of an Os-hydride adduct in aqueous solution by H-1 NMR(-4.2 ppm). Active iminopyridine complexes induced a dramatic increase in the levels of reactive oxygen species (ROS) in A549 lung cancer cells. The anticancer activity may therefore involve interference in the redox signalling pathways in cancer cells by a novel mechanism.

As a new form of carbon, graphene is attracting intense interest as an electrode material with widespread applications. In the present study, the heterogeneous electron transfer (ET) activity of graphene is investigated using scanning electrochemical cell microscopy (SECCM), which allows electrochemical currents to be mapped at high spatial resolution across a surface for correlation with the corresponding structure and properties of the graphene surface. We establish that the rate of heterogeneous ET at graphene increases systematically with the number of graphene layers, and show that the stacking in multilayers also has a subtle influence on ET kinetics.

Scanning electrochemical cell microscopy (SECCM) is a high resolution electrochemical scanning probe technique that employs a dual-barrel theta pipet probe containing electrolyte solution and quasi-reference counter electrodes (QRCE) in each barrel. A thin layer of electrolyte protruding from the tip of the pipet ensures that a gentle meniscus contact is made with a substrate surface, which defines the active surface area of an electrochemical cell. The substrate can be an electrical conductor, semiconductor, or insulator. The main focus here is on the general case where the substrate is a working electrode, and both ion-conductance measurements between the QRCEs in the two barrels and voltammetric/amperometric measurements at the substrate can be made simultaneously. In usual practice, a small perpendicular oscillation of the probe with respect to the substrate is employed, so that an alternating conductance current (ac) develops, due to the change in the dimensions of the electrolyte contact (and hence resistance), as well as the direct conductance current (dc). It is shown that the dc current can be predicted for a fixed probe by solving the Nernst-Planck equation and that the ac response can also be derived from this response. Both responses are shown to agree well with experiment. It is found that the pipet geometry plays an important role in controlling the dc conductance current and that this is easily measured by microscopy. A key feature of SECCM is that mass transport to the substrate surface is by diffusion and, for charged analytes, ion migration which can be controlled and varied quantifiably via the bias between the two QRCEs. For a working electrode substrate this means that charged redox-active analytes can be transported to the electrode/solution interface in a well-defined and controllable manner and that relatively fast heterogeneous electron transfer kinetics can be studied. The factors controlling the voltammetric response are determined by both simulation and experiment. Experiments demonstrate the realization of simultaneous quantitative voltammetric and ion conductance measurements and also identify a general rule of thumb that the surface contacted by electrolyte is of the order of the pipet probe dimensions.

Carbon nanotubes have attracted considerable interest for electrochemical, electrocatalytic, and sensing applications, yet there remains uncertainty concerning the intrinsic electrochemical (EC) activity. In this study, we use scanning electrochemical cell microscopy (SECCM) to determine local heterogeneous electron transfer (HET) kinetics in a random 2D network of single-walled carbon nanotubes (SWNTs) on an Si/SiO 2 substrate. The high spatial resolution of SECCM, which employs a mobile nanoscale EC cell as a probe for imaging, enables us to sample the responses of individual portions of a wide range of SWNTs within this complex arrangement. Using two redox processes, the oxidation of ferrocenylmethyl trimethylammonium and the reduction of ruthenium (III) hexaamine, we have obtained conclusive evidence for the high intrinsic EC activity of the sidewalls of the large majority of SWNTs in networks. Moreover, we show that the ends of SWNTs and the points where two SWNTs cross do not show appreciably different HET kinetics relative to the sidewall. Using finite element method modeling, we deduce standard rate constants for the two redox couples and demonstrate that HET based solely on characteristic defects in the SWNT side wall is highly unlikely. This is further confirmed by the analysis of individual line profiles taken as the SECCM probe scans over an SWNT. More generally, the studies herein demonstrate SECCM to be a powerful and versatile method for activity mapping of complex electrode materials under conditions of high mass transport, where kinetic assignments can be made with confidence.

We introduce a multiprobe platform for the investigation of single-walled carbon nanotubes (SWNTs) that allows the electrochemical response of an individual SWNT to be mapped at high spatial resolution and correlated directly with the intrinsic electronic and structural properties. With this approach, we develop a detailed picture of the factors controlling electrochemistry at SWNTs and propose a definitive model that has major implications for future architectures of SWNT electrode devices.

The use of intermittent contact-scanning electrochemical microscopy (IC-SECM) in diffusion-limited amperometric mode to visualize and quantify mass transport through multiporous membranes is described using dentin as a model example. The IC mode of SECM employs the damping of a vertically modulated ultramicroelectrode (UME) to achieve positioning close to the receptor side of a membrane. In this way the UME can detect electroactive species close to the pore exit. A key aspect of IC-SECM is that in addition to the direct current (dc) from the diffusion-limited detection of the analyte, an alternating current (ac) also develops due to the motion of the probe. It demonstrates that this ac signal enhances the spatial resolution of SECM detection and allows the hydrodynamic flow of species to be detected from individual closely spaced pores. The experimental deductions are supported by three-dimensional finite element modeling which allows IC-SECM current maps to be analyzed to reveal transport rates through individual pores. The method described should be widely applicable to multiporous membrane transport.

The intrinsic dissolution activity of the basal (010) and edge (001) surfaces of gypsum and polycrystalline calcium sulfate anhydrite crystals has been investigated, under far from equilibrium conditions, via the channel flow cell (CFC) method with off-line inductively coupled plasma-mass spectrometry (ICP-MS) for the measurement of dissolved Ca2+ from the crystal surface. This approach allows measurements to be made over a wide range of flow rates so that the importance of mass transport versus surface kinetics can be elucidated. Complementary quantitative modeling of the dissolution process was carried out by formulating convective diffusive equations that describe mass transport in the CFC, coupled to a boundary condition for dissolution of the crystal surface. We found that a linear rate law applied, and intrinsic dissolution fluxes were deduced. The following dissolution fluxes, J(o) = k(diss) x c(eq) were measured, where k(diss) is the dissolution rate constant and c(eq) the calcium sulfate concentration in saturated solution: 5.7 (+/- 1.4) x 10(-9) mol cm(-2) s(-1) for basal plane gypsum and 4.1 (+/- 0.7) x 10(-9) mol cm(-2) s(-1) for calcium sulfate anhydrite. Edge plane gypsum, under the experimental conditions applied, was found to dissolve at a mass transport-controlled rate. The effects of t-tartaric acid, d-tartaric acid, and sodium trimetaphosphate (STMP) as important potential additives of the dissolution process of basal plane gypsum were investigated. It was found that the tartaric acids had little effect but that STMP significantly retarded gypsum dissolution with J(o) = 1.6 (+/- 0.6) x 10(-9) mol cm(-2) s(-1) (5 mM STMP solution). The mode of action of STMP was further elucidated via etch pit morphology studies.