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Determining electrocatalytic activity for reactions that involve reactants with limited solubility presents a significant challenge due to the reduced mass-transport to the electrocatalyst surface. This limitation is seen in important reactions such as the oxygen reduction reaction, nitrogen reduction reaction, and carbon dioxide reduction reaction. We introduce a new approach, which we call scanning bubble electrochemical microscopy, to enable the detection and high-resolution mapping of electrocatalytic activity with low-solubility reactants at high mass-transport rates. Using a scanning probe approach, a dual-barreled nanopipette is used to precisely deliver the gas-phase reactant within micrometers of an electrocatalyst surface, which results in high mass-transport rates at the electrocatalyst surface directly under the probe. We demonstrate the scanning bubble electrochemical microscopy approach by mapping the oxygen reduction reaction on model platinum microelectrode surfaces. We anticipate that scanning bubble electrochemical microscopy will provide an effective tool for measuring the electrocatalytic activity of reactants that have limited solubility.
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Tenofovir (TNF) is a nucleotide reverse transcriptase inhibitor used as an antiviral medication to treat human immunodeficiency virus (HIV) and hepatitis B virus infections. The extensive use of TNF can result in its release into the environment, and there is growing interest in developing simple and cost-effective methods for detecting TNF. We report that the electrochemical dissolution of gold in a chloride ion-containing electrolyte is suppressed in the presence of TNF. The quenching of the gold electrodissolution response is the result of the adsorption of TNF onto the gold surface. A simple analysis shows that we can relate the degree of TNF surface coverage to the relative size of the quenching of the gold electrodissolution response and follow the time-dependent absorption of TNF onto the gold electrode surface.
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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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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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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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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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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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Técnicas Eletroquímicas , Microscopia Eletroquímica de Varredura , Energia Solar , Eletrólitos/química , Ouro/química , Líquidos Iônicos/química , Processos Fotoquímicos , Polímeros/química , Titânio/químicaRESUMO
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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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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Técnicas Eletroquímicas/instrumentação , Íons/química , Microscopia/instrumentação , Eletrodos , Eletrólitos/química , Desenho de Equipamento , Ouro/química , Concentração de Íons de Hidrogênio , Líquidos Iônicos/química , Nanotubos de Carbono/ultraestruturaRESUMO
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.
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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.
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Técnicas Eletroquímicas/métodos , Nanotubos de Carbono/química , Simulação por Computador , Eletroquímica , Eletrodos , Transporte de Elétrons/fisiologia , Análise de Elementos Finitos , Microscopia/métodos , Oxirredução , Dióxido de Silício/químicaRESUMO
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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Técnicas Eletroquímicas , Nanotecnologia , Técnicas Eletroquímicas/instrumentação , Eletrodos , Nanotecnologia/instrumentação , Propriedades de SuperfícieRESUMO
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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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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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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Electrochemical (EC) carbon dioxide (CO2) reduction, where CO2 is converted to value-added products such as fuel precursors, plays a key role in helping the world's energy system reach net-zero carbon emissions. Simulations of EC cells provide valuable insight into their operation since detailed experimental results on short length and time scales are difficult to obtain. In this work, we construct a 1D simulation of a membrane-electrode-assembly EC cell for CO2 reduction, using a porous silver gas diffusion cathode. We run the simulation under different electrolyte conditions, showing how the cell performance is affected. We then perform a sensitivity analysis of all input parameters to the simulation, which has not been presented before in the literature. We show that the CO partial current density (i CO) is significantly affected by each input parameter of the simulation. i CO is most sensitive to EC kinetic parameters (i 0/α) of all EC reactions, with a 1% change in α resulting in up to 6% change in i CO. Since there is uncertainty associated with the value of each input parameter, this indicates that infidelity between experiment and simulation is likely, and thus, caution should be practiced when comparing experimental results to simulation results. Further, we show that the large range of conditions simulated in literature helps to explain the large variance in reported values of i 0 and α. The results of this paper demonstrate the potential of sensitivity analysis methods to quickly optimize aspects of cell performance (CO2 utilization, Faradaic efficiency, etc.).
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The ability of neurons to modulate synaptic strength underpins synaptic plasticity, learning and memory, and adaptation to sensory experience. Despite the importance of synaptic adaptation in directing, reinforcing, and revising the behavioral response to environmental influences, the cellular and molecular mechanisms underlying synaptic adaptation are far from clear. Brain-derived neurotrophic factor (BDNF) is a prime initiator of structural and functional synaptic adaptation. However, the signaling cascade activated by BDNF to initiate these adaptive changes has not been elucidated. We have previously shown that BDNF activates mitogen- and stress-activated kinase 1 (MSK1), which regulates gene transcription via the phosphorylation of both CREB and histone H3. Using mice with a kinase-dead knock-in mutation of MSK1, we now show that MSK1 is necessary for the upregulation of synaptic strength in response to environmental enrichment in vivo. Furthermore, neurons from MSK1 kinase-dead mice failed to show scaling of synaptic transmission in response to activity deprivation in vitro, a deficit that could be rescued by reintroduction of wild-type MSK1. We also show that MSK1 forms part of a BDNF- and MAPK-dependent signaling cascade required for homeostatic synaptic scaling, which likely resides in the ability of MSK1 to regulate cell surface GluA1 expression via the induction of Arc/Arg3.1. These results demonstrate that MSK1 is an integral part of a signaling pathway that underlies the adaptive response to synaptic and environmental experience. MSK1 may thus act as a key homeostat in the activity- and experience-dependent regulation of synaptic strength.
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Homeostase/genética , Plasticidade Neuronal/genética , Neurônios/metabolismo , Proteínas Quinases S6 Ribossômicas 90-kDa/metabolismo , Sinapses/fisiologia , Análise de Variância , Animais , Animais Recém-Nascidos , Fator Neurotrófico Derivado do Encéfalo/farmacologia , Células Cultivadas , Proteínas do Citoesqueleto/metabolismo , Espinhas Dendríticas/fisiologia , Meio Ambiente , Inibidores Enzimáticos/farmacologia , Potenciais Pós-Sinápticos Excitadores/efeitos dos fármacos , Potenciais Pós-Sinápticos Excitadores/genética , Feminino , Regulação da Expressão Gênica/efeitos dos fármacos , Regulação da Expressão Gênica/genética , Proteínas de Fluorescência Verde/genética , Hipocampo/citologia , Homeostase/efeitos dos fármacos , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Transgênicos , Proteínas do Tecido Nervoso/metabolismo , Plasticidade Neuronal/efeitos dos fármacos , Neurônios/ultraestrutura , Técnicas de Patch-Clamp , Mutação Puntual/genética , Receptores de AMPA/metabolismo , Proteínas Quinases S6 Ribossômicas 90-kDa/genética , Transdução de Sinais/efeitos dos fármacos , Transdução de Sinais/genética , Bloqueadores dos Canais de Sódio/farmacologia , Sinapses/genética , Tetrodotoxina/farmacologia , Fatores de TempoRESUMO
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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Microscopia/métodos , Eletroquímica , Eletrodos , Ouro/química , Microscopia/instrumentação , Platina/química , Soluções , Propriedades de SuperfícieRESUMO
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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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.