Publications by authors named "Kim McKelvey"

39 Publications

Enhancing Lithium Insertion with Electrostatic Nanoconfinement in a Lithography Patterned Precision Cell.

ACS Nano 2019 Jul 5;13(7):8481-8489. Epub 2019 Jul 5.

Department of Electrical Engineering , Yale University , New Haven , Connecticut 06511 , United States.

The rapidly growing demand for portable electronics, electric vehicles, and grid storage drives the pursuit of high-performance electrical energy storage (EES). A key strategy for improving EES performance is exploiting nanostructured electrodes that present nanoconfined environments of adjacent electrolytes, with the goal to decrease ion diffusion paths and increase active surface areas. However, fundamental gaps persist in understanding the interface-governed electrochemistry in such nanoconfined geometries, in part because of the imprecise and variable dimension control. Here, we report quantification of lithium insertion under nanoconfinement of the electrolyte in a precise lithography-patterned nanofluidic cell. We show a mechanism that enhances ion insertion under nanoconfinement, namely, selective ion accumulation when the confinement length is comparable to the electrical double layer thickness. The nanofabrication approach with uniform and accurate dimensional control provides a versatile model system to explore fundamental mechanisms of nanoscale electrochemistry, which could have an impact on practical energy storage systems.
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http://dx.doi.org/10.1021/acsnano.9b04390DOI Listing
July 2019

Single Ag nanoparticle collisions within a dual-electrode micro-gap cell.

Faraday Discuss 2018 10;210(0):189-200

Department of Chemistry, University of Utah, Salt Lake City, UT 84112, USA.

An adjustable width (between 600 nm and 20 μm) gap between two Au microelectrodes is used to probe the electrodissolution dynamics of single Ag nanoparticles. One Au microelectrode is used to drive the oxidation and subsequent dissolution of a single Ag nanoparticle, which displays a multi-peak oxidation behavior, while a second Au microelectrode is used to collect the Ag+ that is produced. Careful analysis of the high temporal resolution current-time traces reveals capacitive coupling between electrodes due to the sudden injection of Ag+ ions into the gap between the electrodes. The current-time traces allow measurement of the effect of citrate concentration on the electrodissolution dynamics of a single Ag nanoparticle, which reveals that the presence of 2 mM citrate significantly slows down the release of Ag+. Intriguingly, these experiments also reveal that only a portion (ca. 50%) of the oxidized Ag nanoparticle is released as free Ag+ regardless of citrate concentration.
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http://dx.doi.org/10.1039/c8fd00014jDOI Listing
October 2018

Method for Dynamically Detecting Secretions from Single Cells Using a Nanopore.

Nano Lett 2018 07 13;18(7):4263-4272. Epub 2018 Jun 13.

Secreted proteins mediate cell-to-cell communications. Thus, eavesdropping on the secretome could reveal the cellular phenotype, but it is challenging to detect the proteins because they are secreted only in minute amounts and then diluted in blood plasma or contaminated by cell culture medium or the lysate. In this pilot study, it is demonstrated that secretions from single cancer cells can be detected and dynamically analyzed through measurements of blockades in the electrolytic current due to single molecules translocating through a nanopore in a thin inorganic membrane. It is established that the distribution of blockades can be used to differentiate three different cancer cell lines (U937, MDA-MB-231, and MCF-7) in real time and quickly (<20 s). Importantly, the distinctive blockades associated with the chemokine CCL5, a prognostic factor for disease progression in breast cancer, along with other low-mass biomarkers of breast cancer (PI3, TIMP1, and MMP1) were identified in the context of the secretome of these three cell types, tracked with time, and used to provide information on the cellular phenotype.
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http://dx.doi.org/10.1021/acs.nanolett.8b01257DOI Listing
July 2018

Selective increase in CO electroreduction activity at grain-boundary surface terminations.

Science 2017 12;358(6367):1187-1192

Department of Chemistry, Stanford University, 337 Campus Drive, Stanford, CA 94305, USA.

Altering a material's catalytic properties requires identifying structural features that give rise to active surfaces. Grain boundaries create strained regions in polycrystalline materials by stabilizing dislocations and may provide a way to create high-energy surfaces for catalysis that are kinetically trapped. Although grain-boundary density has previously been correlated with catalytic activity for some reactions, direct evidence that grain boundaries create surfaces with enhanced activity is lacking. We used a combination of bulk electrochemical measurements and scanning electrochemical cell microscopy with submicrometer resolution to show that grain-boundary surface terminations in gold electrodes are more active than grain surfaces for electrochemical carbon dioxide (CO) reduction to carbon monoxide (CO) but not for the competing hydrogen (H) evolution reaction. The catalytic footprint of the grain boundary is commensurate with its dislocation-induced strain field, providing a strategy for broader exploitation of grain-boundary effects in heterogeneous catalysis.
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http://dx.doi.org/10.1126/science.aao3691DOI Listing
December 2017

Three-Dimensional Super-resolution Imaging of Single Nanoparticles Delivered by Pipettes.

ACS Nano 2017 10 5;11(10):10529-10538. Epub 2017 Oct 5.

Department of Chemistry, Temple University , Philadelphia, Pennsylvania 19122, United States.

Controlled three-dimensional positioning of nanoparticles is achieved by delivering single fluorescent nanoparticles from a nanopipette and capturing them at well-defined regions of an electrified substrate. To control the position of single nanoparticles, the force of the pressure-driven flow from the pipette is balanced by the attractive electrostatic force at the substrate, providing a strategy by which nanoparticle trajectories can be manipulated in real time. To visualize nanoparticle motion, a resistive-pulse electrochemical setup is coupled with an optical microscope, and nanoparticle trajectories are tracked in three dimensions using super-resolution fluorescence imaging to obtain positional information with precision in the tens of nanometers. As the particles approach the substrate, the diffusion kinetics are analyzed and reveal either subdiffusive (hindered) or superdiffusive (directed) motion depending on the electric field at the substrate and the pressure-driven flow from the pipette. By balancing the effects of the forces exerted on the particle by the pressure and electric fields, controlled, real-time manipulation of single nanoparticle trajectories is achieved. The developed approach has implications for a variety of applications such as surface patterning and drug delivery using colloidal nanoparticles.
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http://dx.doi.org/10.1021/acsnano.7b05902DOI Listing
October 2017

Fabrication, Testing, and Simulation of All-Solid-State Three-Dimensional Li-Ion Batteries.

ACS Appl Mater Interfaces 2016 Nov 18;8(47):32385-32391. Epub 2016 Nov 18.

Department of Chemistry, University of Utah , Salt Lake City, Utah 84112, United States.

Demonstration of three-dimensional all-solid-state Li-ion batteries (3D SSLIBs) has been a long-standing goal for numerous researchers in the battery community interested in developing high power and high areal energy density storage solutions for a variety of applications. Ideally, the 3D geometry maximizes the volume of active material per unit area, while keeping its thickness small to allow for fast Li diffusion. In this paper, we describe experimental testing and simulation of 3D SSLIBs fabricated using materials and thin-film deposition methods compatible with semiconductor device processing. These 3D SSLIBs consist of Si microcolumns onto which the battery layers are sequentially deposited using physical vapor deposition. The power performance of the 3D SSLIBs lags significantly behind that of similarly prepared planar SSLIBs. Analysis of the experimental results using finite element modeling indicates that the origin of the poor power performance is the structural inhomogeneity of the 3D SSLIB, coupled with low electrolyte ionic conductivity and diffusion rate in the cathode, which lead to highly nonuniform internal current density distribution and poor cathode utilization.
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http://dx.doi.org/10.1021/acsami.6b12244DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5526591PMC
November 2016

Resistive Pulse Delivery of Single Nanoparticles to Electrochemical Interfaces.

J Phys Chem Lett 2016 Oct 22;7(19):3920-3924. Epub 2016 Sep 22.

Department of Chemistry, University of Utah , Salt Lake City, Utah 84112, United States.

An experimental system for controlling and interrogating the collisions of individual nanoparticles at electrode/electrolyte interfaces is described. A nanopipet positioned over a 400 nm radius Pt ultramicroelectrode is used to deliver individual nanoparticles, via pressure-driven solution flow, to the underlying electrode, where the nanoparticles undergo collisions and are detected electrochemically. High-velocity collisions result in elastic collisions of negatively charged polystyrene nanospheres at the Pt/water interface, while low-velocity collisions result in nanoparticle adsorption ("sticky" collisions). The ability to position the nanopipet with respect to the underlying ultramicroelectrode also allows the time between particle release from the nanopipet and electrode collision to be investigated as a function of nanopipet-electrode separation, d. The time between release and collision of the nanoparticle is found to be proportional to d, in excellent agreement with an analytical expression for convective fluid flow from a pipet orifice.
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http://dx.doi.org/10.1021/acs.jpclett.6b01873DOI Listing
October 2016

Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

J Colloid Interface Sci 2016 Aug 13;476:94-102. Epub 2016 May 13.

Electrochemistry and Interfaces Group, Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK. Electronic address:

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 (1mM 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 Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-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 10-20nm 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.
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http://dx.doi.org/10.1016/j.jcis.2016.05.018DOI Listing
August 2016

Simultaneous Interfacial Reactivity and Topography Mapping with Scanning Ion Conductance Microscopy.

Anal Chem 2016 Mar 10;88(5):2838-46. Epub 2016 Feb 10.

Department of Chemistry, University of Warwick , Coventry, CV4 7AL, United Kingdom.

Scanning ion conductance microscopy (SICM) is a powerful technique for imaging the topography of a wide range of materials and interfaces. In this report, we develop the use and scope of SICM, showing how it can be used for mapping spatial distributions of ionic fluxes due to (electro)chemical reactions occurring at interfaces. The basic idea is that there is a change of ion conductance inside a nanopipet probe when it approaches an active site, where the ionic composition is different to that in bulk solution, and this can be sensed via the current flow in the nanopipet with an applied bias. Careful tuning of the tip potential allows the current response to be sensitive to either topography or activity, if desired. Furthermore, the use of a distance modulation SICM scheme allows reasonably faithful probe positioning using the resulting ac response, irrespective of whether there is a reaction at the interface that changes the local ionic composition. Both strategies (distance modulation or tuned bias) allow simultaneous topography-activity mapping with a single channel probe. The application of SICM reaction imaging is demonstrated on several examples, including voltammetric mapping of electrocatalytic reactions on electrodes and high-speed electrochemical imaging at rates approaching 4 s per image frame. These two distinct approaches provide movies of electrochemical current as a function of potential with hundreds of frames (images) of surface reactivity, to reveal a wealth of spatially resolved information on potential- (and time) dependent electrochemical phenomena. The experimental studies are supported by detailed finite element method modeling that places the technique on a quantitative footing.
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http://dx.doi.org/10.1021/acs.analchem.5b04566DOI Listing
March 2016

Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

Anal Chem 2015 Oct 2;87(20):10450-6. Epub 2015 Oct 2.

Department of Chemistry, University of Warwick , Coventry CV4 7AL, U.K.

Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size.
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http://dx.doi.org/10.1021/acs.analchem.5b02569DOI Listing
October 2015

High-Speed Electrochemical Imaging.

ACS Nano 2015 Sep 26;9(9):8942-52. Epub 2015 Aug 26.

Department of Chemistry, University of Warwick , Coventry CV4 7AL, United Kingdom.

The design, development, and application of high-speed scanning electrochemical probe microscopy is reported. The approach allows the acquisition of a series of high-resolution images (typically 1000 pixels μm(-2)) at rates approaching 4 seconds per frame, while collecting up to 8000 image pixels per second, about 1000 times faster than typical imaging speeds used up to now. The focus is on scanning electrochemical cell microscopy (SECCM), but the principles and practicalities are applicable to many electrochemical imaging methods. The versatility of the high-speed scan concept is demonstrated at a variety of substrates, including imaging the electroactivity of a patterned self-assembled monolayer on gold, visualization of chemical reactions occurring at single wall carbon nanotubes, and probing nanoscale electrocatalysts for water splitting. These studies provide movies of spatial variations of electrochemical fluxes as a function of potential and a platform for the further development of high speed scanning with other electrochemical imaging techniques.
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http://dx.doi.org/10.1021/acsnano.5b02792DOI Listing
September 2015

Voltammetric Scanning Electrochemical Cell Microscopy: Dynamic Imaging of Hydrazine Electro-oxidation on Platinum Electrodes.

Anal Chem 2015 Jun 18;87(11):5782-9. Epub 2015 May 18.

†Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K.

Voltammetric scanning electrochemical cell microscopy (SECCM) incorporates cyclic voltammetry measurements in the SECCM imaging protocol, by recording electrochemical currents in a wide potential window at each pixel in a map. This provides much more information compared to traditional fixed potential imaging. Data can be represented as movies (hundreds of frames) of current (over a surface region) at a series of potentials and are highly revealing of subtle variations in electrode activity. Furthermore, by combining SECCM data with other forms of microscopy, e.g. scanning electron microscopy and electron backscatter diffraction data, it is possible to directly relate the current-voltage characteristics to spatial position and surface structure. In this work we use a "hopping mode", where the SECCM pipet probe is translated toward the surface at a series of positions until meniscus contact. Small amounts of residue left on the surface, upon probe retraction, demark the precise area of each measurement. We use these techniques to study hydrazine oxidation on a polycrystalline platinum substrate both in air and in a deaerated environment. In both cases, the detected faradaic current shows a structural dependence on the surface crystallographic orientation. Significantly, in the presence of oxygen (aerated solution) the electrochemical current decreases strongly for almost all grains (crystallographic orientations). The results highlight the flexibility of voltammetric SECCM for electrochemical imaging and present important implications for hydrazine electroanalysis.
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http://dx.doi.org/10.1021/acs.analchem.5b00988DOI Listing
June 2015

Scanning electrochemical cell microscopy platform for ultrasensitive photoelectrochemical imaging.

Anal Chem 2015 Apr 6;87(8):4129-33. Epub 2015 Apr 6.

Department of Chemistry, University of Warwick, Gibbet Hill Rd, Coventry, CV4 7AL United Kingdom.

The development of techniques for nanoscale structure-activity correlations is of major importance for the fundamental understanding and rational design of (photo)electrocatalysts. However, the low conversion efficiency of characteristic materials generates tiny photoelectrochemical currents at the submicrometer to nanoscale, in the fA range, which are challenging to detect and measure accurately. Here, we report the coupling of scanning electrochemical cell microscopy (SECCM) with photoillumination, to create a submicrometer spatial resolution cell that opens up high resolution structure-(photo)activity measurements. We demonstrate the capabilities of the technique as a tool for: (i) high spatial resolution (photo)activity mapping using an ionic liquid electrolyte at a thin film of TiO2 aggregates, commonly used as a photoanode in dye sensitized solar cells (DSSCs) and (ii) in situ (photo)activity measurements of an electropolymerized conjugated polymer on a transparent Au substrate in a controlled atmospheric environment. Quantitative data, including localized (photo)electrochemical transients and external quantum efficiency (EQE), are extracted, and prospects for further technique development and enhancement are outlined.
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http://dx.doi.org/10.1021/acs.analchem.5b00288DOI Listing
April 2015

Quad-barrel multifunctional electrochemical and ion conductance probe for voltammetric analysis and imaging.

Anal Chem 2015 Apr 16;87(7):3566-73. Epub 2015 Mar 16.

Department of Chemistry, University of Warwick, Coventry, CV4 7AL, United Kingdom.

The fabrication and use of a multifunctional electrochemical probe incorporating two independent carbon working electrodes and two electrolyte-filled barrels, equipped with quasi-reference counter electrodes (QRCEs), in the end of a tapered micrometer-scale pipet is described. This "quad-probe" (4-channel probe) was fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barrelled pipet. After filling the open channels with electrolyte solution, a meniscus forms at the end of the probe and covers the two working electrodes. The two carbon electrodes can be used to drive local electrochemical reactions within the meniscus while a bias between the QRCEs in the electrolyte channels provides an ion conductance signal that is used to control and position the meniscus on a surface of interest. When brought into contact with a surface, localized high resolution amperometric imaging can be achieved with the two carbon working electrodes with a spatial resolution defined by the meniscus contact area. The substrate can be an insulating material or (semi)conductor, but herein, we focus mainly on conducting substrates that can be connected as a third working electrode. Studies using both aqueous and ionic liquid electrolytes in the probe, together with gold and individual single walled carbon nanotube samples, demonstrate the utility of the technique. Substrate generation-dual tip collection measurements are shown to be characterized by high collection efficiencies (approaching 100%). This hybrid configuration of scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) should be powerful for future applications in electrode mapping, as well as in studies of insulating materials as demonstrated by transient spot redox-titration measurements at an electrostatically charged Teflon surface and at a pristine calcite surface, where a functionalized probe is used to follow the immediate pH change due to dissolution.
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http://dx.doi.org/10.1021/acs.analchem.5b00379DOI Listing
April 2015

Surface charge mapping with a nanopipette.

J Am Chem Soc 2014 Oct 19;136(39):13735-44. Epub 2014 Sep 19.

Department of Chemistry and ‡MOAC Doctoral Training Centre, University of Warwick , Coventry, U.K. CV4 7AL.

Nanopipettes are emerging as simple but powerful tools for probing chemistry at the nanoscale. In this contribution the use of nanopipettes for simultaneous surface charge mapping and topographical imaging is demonstrated, using a scanning ion conductance microscopy (SICM) format. When a nanopipette is positioned close to a surface in electrolyte solution, the direct ion current (DC), driven by an applied bias between a quasi-reference counter electrode (QRCE) in the nanopipette and a second QRCE in the bulk solution, is sensitive to surface charge. The charge sensitivity arises because the diffuse double layers at the nanopipette and the surface interact, creating a perm-selective region which becomes increasingly significant at low ionic strengths (10 mM 1:1 aqueous electrolyte herein). This leads to a polarity-dependent ion current and surface-induced rectification as the bias is varied. Using distance-modulated SICM, which induces an alternating ion current component (AC) by periodically modulating the distance between the nanopipette and the surface, the effect of surface charge on the DC and AC is explored and rationalized. The impact of surface charge on the AC phase (with respect to the driving sinusoidal signal) is highlighted in particular; this quantity shows a shift that is highly sensitive to interfacial charge and provides the basis for visualizing charge simultaneously with topography. The studies herein highlight the use of nanopipettes for functional imaging with applications from cell biology to materials characterization where understanding surface charge is of key importance. They also provide a framework for the design of SICM experiments, which may be convoluted by topographical and surface charge effects, especially for small nanopipettes.
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http://dx.doi.org/10.1021/ja506139uDOI Listing
October 2014

Positionable vertical microfluidic cell based on electromigration in a theta pipet.

Langmuir 2014 Aug 15;30(33):10011-8. Epub 2014 Aug 15.

Department of Chemistry, and ‡MOAC Doctoral Training Centre, University of Warwick , Coventry CV4 7AL, United Kingdom.

A microscale vertical fluidic cell system has been implemented, based on a simple theta pipet pulled to a sharp point (ca. 10-20 μm 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 μm 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.
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http://dx.doi.org/10.1021/la5020412DOI Listing
August 2014

Molecular functionalization of graphite surfaces: basal plane versus step edge electrochemical activity.

J Am Chem Soc 2014 Aug 1;136(32):11444-51. Epub 2014 Aug 1.

Department of Chemistry, University of Warwick , Coventry CV4 7AL, United Kingdom.

The chemical functionalization of carbon surfaces has myriad applications, from tailored sensors to electrocatalysts. Here, the adsorption and electrochemistry of anthraquinone-2,6-disulfonate (AQDS) is studied on highly oriented pyrolytic graphite (HOPG) as a model sp(2) surface. A major focus is to elucidate whether adsorbed electroactive AQDS can be used as a marker of step edges, which have generally been regarded as the main electroactive sites on graphite electrode surfaces. First, the macroscopic electrochemistry of AQDS is studied on a range of surfaces differing in step edge density by more than 2 orders of magnitude, complemented with ex situ tapping mode atomic force microscopy (AFM) data. These measurements show that step edges have little effect on the extent of adsorbed electroactive AQDS. Second, a new fast scan cyclic voltammetry protocol carried out with scanning electrochemical cell microscopy (SECCM) enables the evolution of AQDS adsorption to be followed locally on a rapid time scale. Subsequent AFM imaging of the areas probed by SECCM allows a direct correlation of the electroactive adsorption coverage and the actual step edge density of the entire working area. The amount of adsorbed electroactive AQDS and the electron transfer kinetics are independent of the step edge coverage. Last, SECCM reactive patterning is carried out with complementary AFM measurements to probe the diffusional electroactivity of AQDS. There is essentially uniform and high activity across the basal surface of HOPG. This work provides new methodology to monitor adsorption processes at surfaces and shows unambiguously that there is no correlation between the step edge density of graphite surfaces and the observed coverage of electroactive AQDS. The electroactivity is dominated by the basal surface, and studies that have used AQDS as a marker of steps need to be revised.
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http://dx.doi.org/10.1021/ja505266dDOI Listing
August 2014

Measurement of the efficacy of calcium silicate for the protection and repair of dental enamel.

J Dent 2014 Jun;42 Suppl 1:S21-9

Unilever Oral Care, Quarry Road East, Bebington, Wirral CH63 3JW, UK.

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.
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http://dx.doi.org/10.1016/S0300-5712(14)50004-8DOI Listing
June 2014

Bias modulated scanning ion conductance microscopy.

Anal Chem 2014 Apr 21;86(7):3639-46. Epub 2014 Mar 21.

Department of Chemistry and ‡MOAC Doctoral Training Centre, University of Warwick , Coventry, CV4 7AL, United Kingdom.

Nanopipets are versatile tools for nanoscience, particularly when used in scanning ion conductance microscopy (SICM) to determine, in a noncontact manner, the topography of a sample. We present a new method, applying an oscillating bias between a quasi-reference counter electrode (QRCE) in the SICM nanopipet probe and a second QRCE in the bulk solution, to generate a feedback signal to control the distance between the end of a nanopipet and a surface. Both the amplitude and phase of the oscillating ion current, induced by the oscillating bias and extracted using a phase-sensitive detector, are shown to be sensitive to the probe-surface distance and are used to provide stable feedback signals. The phase signal is particularly sensitive at high frequencies of the oscillating bias (up to 30 kHz herein). This development eliminates the need to physically oscillate the probe to generate an oscillating ion current feedback signal, as needed for conventional SICM modes. Moreover, bias modulation allows a feedback signal to be generated without any net ion current flow, ensuring that any polarization of the quasi reference counter electrodes, electro-osmotic effects, and perturbations of the supporting electrolyte composition are minimized. Both feedback signals, magnitude and phase, are analyzed through approach curve measurements to different surfaces at a range of distinct frequencies and via impedance measurements at different distances from a surface. The bias modulated response is readily understood via a simple equivalent circuit model. Bias modulated (BM)-SICM is compared to conventional SICM imaging through measurements of substrates with distinct topographical features and yields equivalent results. Finally, BM-SICM with both amplitude and phase feedback is used for topographical imaging of subtle etch features in a calcite crystal surface. The 2 modes yield similar results, but phase-detection opens up the prospect of faster imaging.
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http://dx.doi.org/10.1021/ac5003118DOI Listing
April 2014

Dual-barrel conductance micropipet as a new approach to the study of ionic crystal dissolution kinetics.

Langmuir 2013 Dec 5;29(50):15565-72. Epub 2013 Dec 5.

Department of Chemistry and ‡MOAC Doctoral Training Centre, University of Warwick , Gibbet Hill Road, Coventry CV4 7AL, United Kingdom.

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.
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http://dx.doi.org/10.1021/la403630uDOI Listing
December 2013

Fabrication and characterization of dual function nanoscale pH-scanning ion conductance microscopy (SICM) probes for high resolution pH mapping.

Anal Chem 2013 Sep 22;85(17):8070-4. Epub 2013 Aug 22.

Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK.

The easy fabrication and use of nanoscale dual function pH-scanning ion conductance microscopy (SICM) probes is reported. These probes incorporate an iridium oxide coated carbon electrode for pH measurement and an SICM barrel for distance control, enabling simultaneous pH and topography mapping. These pH-SICM probes were fabricated rapidly from laser pulled theta quartz pipets, with the pH electrode prepared by in situ carbon filling of one of the barrels by the pyrolytic decomposition of butane, followed by electrodeposition of a thin layer of hydrous iridium oxide. The other barrel was filled with an electrolyte solution and Ag/AgCl electrode as part of a conductance cell for SICM. The fabricated probes, with pH and SICM sensing elements typically on the 100 nm scale, were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and various electrochemical measurements. They showed a linear super-Nernstian pH response over a range of pH (pH 2-10). The capability of the pH-SICM probe was demonstrated by detecting both pH and topographical changes during the dissolution of a calcite microcrystal in aqueous solution. This system illustrates the quantitative nature of pH-SICM imaging, because the dissolution process changes the crystal height and interfacial pH (compared to bulk), and each is sensitive to the rate. Both measurements reveal similar dissolution rates, which are in agreement with previously reported literature values measured by classical bulk methods.
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http://dx.doi.org/10.1021/ac401883nDOI Listing
September 2013

Fabrication, characterization, and functionalization of dual carbon electrodes as probes for scanning electrochemical microscopy (SECM).

Anal Chem 2013 Aug 8;85(15):7519-26. Epub 2013 Jul 8.

Molecular Organisation and Assembly in Cells (MOAC) Doctoral Training Centre, School of Life Sciences, University of Warwick, Coventry, UK.

Dual carbon electrodes (DCEs) are quickly, easily, and cheaply fabricated by depositing pyrolytic carbon into a quartz theta nanopipet. The size of DCEs can be controlled by adjusting the pulling parameters used to make the nanopipet. When operated in generation/collection (G/C) mode, the small separation between the electrodes leads to reasonable collection efficiencies of ca. 30%. A three-dimensional finite element method (FEM) simulation is developed to predict the current response of these electrodes as a means of estimating the probe geometry. Voltammetric measurements at individual electrodes combined with generation/collection measurements provide a reasonable guide to the electrode size. DCEs are employed in a scanning electrochemical microscopy (SECM) configuration, and their use for both approach curves and imaging is considered. G/C approach curve measurements are shown to be particularly sensitive to the nature of the substrate, with insulating surfaces leading to enhanced collection efficiencies, whereas conducting surfaces lead to a decrease of collection efficiency. As a proof-of-concept, DCEs are further used to locally generate an artificial electron acceptor and to follow the flux of this species and its reduced form during photosynthesis at isolated thylakoid membranes. In addition, 2-dimensional images of a single thylakoid membrane are reported and analyzed to demonstrate the high sensitivity of G/C measurements to localized surface processes. It is finally shown that individual nanometer-size electrodes can be functionalized through the selective deposition of platinum on one of the two electrodes in a DCE while leaving the other one unmodified. This provides an indication of the future versatility of this type of probe for nanoscale measurements and imaging.
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http://dx.doi.org/10.1021/ac401476zDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3971958PMC
August 2013

Quantitative local photosynthetic flux measurements at isolated chloroplasts and thylakoid membranes using scanning electrochemical microscopy (SECM).

J Phys Chem B 2013 Jul 20;117(26):7878-88. Epub 2013 Jun 20.

Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL.

Scanning electrochemical microscopy (SECM) offers a fast and quantitative method to measure local fluxes within photosynthesis. In particular, we have measured the flux of oxygen and ferrocyanide (Fe(CN)6(4-)), from the artificial electron acceptor ferricyanide (Fe(CN)6(3-)), using a stationary ultramicroelectrode at chloroplasts and thylakoid membranes (sourced from chloroplasts). Oxygen generation at films of chloroplasts and thylakoid membranes was detected directly during photosynthesis, but in the case of thylakoid membranes, this switched to sustained oxygen consumption at longer illumination times. An initial oxygen concentration spike was detected over both chloroplast and thylakoid membrane films, and the kinetics of the oxygen generation were extracted by fitting the experimental data to a finite element method (FEM) simulation. In contrast to previous work, the oxygen generation spike was attributed to the limited size of the plastoquinone pool, a key component in the linear electron transport pathway and a contributing factor in photoinhibition. Finally, the mobile nature of the SECM probe, and its high spatial resolution, also allowed us to detect ferrocyanide produced from a single thylakoid membrane. These results further demonstrate the power of SECM for localized flux measurements in biological processes, in this case photosynthesis, and that the high time resolution, combined with FEM simulations, allows the elucidation of quantitative kinetic information.
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http://dx.doi.org/10.1021/jp403048fDOI Listing
July 2013

Scanning electrochemical cell microscopy: a versatile technique for nanoscale electrochemistry and functional imaging.

Annu Rev Anal Chem (Palo Alto Calif) 2013 1;6:329-51. Epub 2013 Apr 1.

Department of Chemistry, University ofWarwick, Coventry CV4 7AL, United Kingdom.

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.
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http://dx.doi.org/10.1146/annurev-anchem-062012-092650DOI Listing
October 2013

Meniscus confined fabrication of multidimensional conducting polymer nanostructures with scanning electrochemical cell microscopy (SECCM).

Chem Commun (Camb) 2013 Apr;49(29):2986-8

Department of Chemistry, University of Warwick, Coventry, UK.

Scanning electrochemical cell microscopy (SECCM) is demonstrated as a new approach for the construction of extended multi-dimensional conducting polymer (polyaniline) nanostructures, making use of a mobile dual-channel theta pipette cell to control and monitor the location, rate and extent of electropolymerisation.
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http://dx.doi.org/10.1039/c3cc00104kDOI Listing
April 2013

Hopping intermittent contact-scanning electrochemical microscopy (HIC-SECM): visualizing interfacial reactions and fluxes from surfaces to bulk solution.

Anal Chem 2013 Mar 25;85(5):2937-44. Epub 2013 Feb 25.

Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL.

Hopping intermittent contact-scanning electrochemical microscopy (HIC-SECM) is introduced as a powerful new technique for the quantitative visualization of redox activity and concentration at and above a surface of interest. HIC-SECM combines a hopping imaging mode, in which data are acquired at a tip as a function of distance (z) from the surface, at a series of x, y pixels across the surface, using the principles of intermittent contact to provide a nonelectrochemical means of determining when the tip and the substrate come into contact. The implementation of HIC-SECM is described, and SECM feedback measurements in three-dimensional (3D) space over a gold band array are presented. To demonstrate the generality of the methodology, flux imaging is also carried out over a Pt-disk ultramicroelectrode (UME) in the feedback mode and substrate generation/tip collection mode. The type of information that can be extracted from the data sets acquired include x-y current maps at a well-defined tip-substrate separation (parallel to the surface), x-z current maps (normal to the surface), 3D x-y-z profiles, approach curves at particular spots on the surface of interest, and surface topography. Moreover, because HIC-SECM utilizes an oscillating probe, alternating current data are also obtained that greatly enhances the information content compared to other types of electrochemical imaging. Furthermore, interfacial fluxes are ubiquitous in chemistry and allied areas, and HIC-SECM opens up the possibility of detailed flux visualization in three dimensions for many physicochemical processes.
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http://dx.doi.org/10.1021/ac303642pDOI Listing
March 2013