Electrochemical Scanning Probe Research Articles

(Invited) Scanning Gel Electrochemical Microscopy: Towards Biological Applications?

Scanning electrochemical probe techniques have been developed in the last 30 years for measuring spatially localized electrochemistry at micro and nano scale. Here, we will present a recently developed tool, namely Scanning Gel Electrochemical Microscopy, for imaging the electrochemical reactivity of surfaces and patterning surfaces by local electrodeposition. The concept is based on a gel probe that is in soft contact with the sample, allowing electrochemical measurements to be spatially localized in the contact area with gel as electrolyte.1 The physical resolution, or the pixel size, can thus be tuned by pressing or pulling the probe after touching the sample.2 So far, two types of gel probes have been developed: Type I by electrodeposition of chitosan on micro-disk electrodes,1-3 and Type II by “electrodeposition + pulling” on sharpened metal wires.4 Local chronoamperometry, potentiometry and cyclic voltammetry have been carried out, either for imaging or for patterning (complex-shaped) surfaces.1-4 The gel has an advantage of localizing and immobilizing the electrolyte, which “frees” the sample from solution in scanning electrochemical microscopy (SECM) and reduces the wetting in scanning electrochemical cell microscopy (SECCM) as supported by quartz crystal microbalance (QCM) measurements in our recent work.5 Moreover, the excellent biocompatibility of the chitosan-based gel (which can easily immobilize drugs, proteins or bacteria) and the soft contact make SGECM a promising technique for biological applications. In this presentation, we will discuss about the feasibility of measuring different possible responses when a gel probe is in contact with a bio-entity (bacteria, bio-film, etc.) in-situ in its culture media: (1) Transport of redox species through the bio-entity, either from the gel to the culture media or the opposite way; (2) Production of redox mediators by the bio-entity that would be captured by the gel probe; (3) Physical and chemical response of the bio-entity induced by the gel probe. These possibilities will be examined by electrochemical modelling. The recent development on polyvinylalcohol-based gel probes will also be introduced. The work is partially supported by ANR-NRF project MEACT (ANR-20-CE09-0028).

Scanning Electrochemical Probe Lithography for Ultra-Precision Machining of Micro-Optical Elements with Freeform Curved Surface.

Two challenges should be overcome for the ultra-precision machining of micro-optical element with freeform curved surface: one is the intricate geometry, the other is the hard-to-machining optical materials due to their hardness, brittleness or flexibility. Here scanning electrochemical probe lithography (SECPL) is developed, not only to meet the machining need of intricate geometry by 3D direct writing, but also to overcome the above mentioned mechanical properties by an electrochemical material removal mode. Through the electrochemical probe a localized anodic voltage is applied to drive the localized corrosion of GaAs. The material removal rate is obtained as a function of applied voltage, motion rate, scan segment, etc. Based on the material removal function, an arbitrary geometry can be converted to a spatially distributed voltage. Thus, a series of micro-optical element are fabricated with a machining accuracy in the scale of 100 s of nanometers. Notably, the spiral phase plate shows an excellent performance to transfer parallel light to vortex beam. SECPL demonstrates its excellent controllability and accuracy for the ultra-precision machining of micro-optical devices with freeform curved surface, providing an alternative chemical approach besides the physical and mechanical techniques.

Simultaneous Mapping of Electrocatalytic Activity and Selectivity via Hybrid Scanning Electrochemical Probe Microscopy.

Nanoscale scanning electrochemical probe microscopy started to elucidate the heterogeneity of electrocatalytic activity at electrode surfaces. However, understanding the heterogeneity in product selectivity, another crucial aspect of interfacial reactivity, remains challenging. Herein, we introduce a method combining scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) to enable the spatially resolved mapping of both activity and selectivity in electrocatalysis. A dual-channel nanopipette probe was developed: one channel for activity mapping and the other for product detection with a high collection efficiency (>95%) and sensitivity. Simultaneous mapping of activity and selectivity in the oxygen reduction reaction (ORR) is demonstrated. Combined with colocalized crystal orientation mapping, we uncover the local electrocatalytic performance of ORR at different facets on polycrystalline Pt and Au. The high-resolution selectivity mapping enabled by our method with colocalized structural characterization can provide structure-activity-selectivity relationships that are often unavailable in ensemble measurement, holding promise for understanding key structural motifs controlling interfacial reactivity.

Scanning electrochemical probe microscopy: towards the characterization of micro- and nanostructured photocatalytic materials.

Platinum-black (Pt-B) has been demonstrated to be an excellent electrocatalytic material for the electrochemical oxidation of hydrogen peroxide (H2O2). As Pt-B films can be deposited electrochemically, micro- and nano-sized conductive transducers can be modified with Pt-B. Here, we present the potential of Pt-B micro- and sub-micro-sized sensors for the detection and quantification of hydrogen (H2) in solution. Using these microsensors, no sampling step for H2 determination is required and e.g., in photocatalysis, the onset of H2 evolution can be monitored in situ. We present Pt-B-based H2 micro- and sub-micro-sized sensors based on different electrochemical transducers such as microelectrodes and atomic force microscopy (AFM)-scanning electrochemical microscopy (SECM) probes, which enable local measurements e.g., at heterogenized photocatalytically active samples. The microsensors are characterized in terms of limits of detection (LOD), which ranges from 4.0 μM to 30 μM depending on the size of the sensors and the experimental conditions such as type of electrolyte and pH. The sensors were tested for the in situ H2 evolution by light-driven water-splitting, i.e., using ascorbic acid or triethanolamine solutions, showing a wide linear concentration range, good reproducibility, and high sensitivity. Proof-of-principle experiments using Pt-B-modified cantilever-based sensors were performed using a model sample platinum substrate to map the electrochemical H2 evolution along with the topography using AFM-SECM.

Charge-induced deformation of scanning electrolyte before contact.

The recent developments in scanning electrochemical probe techniques focus on the strategy of scanning the electrolyte. For example, scanning electrochemical cell microscopy (SECCM) is based on holding the electrolyte in a glass capillary, while scanning gel electrochemical microscopy (SGECM) immobilizes the gel electrolyte on micro-disk electrodes or etched metal wires. In both SECCM and SGECM, the first and essential step is to bring the electrolyte probe into contact with the sample, which is very often achieved by current feedback with a constant applied potential between the probe and the sample. This work attempts to theoretically analyse the deformation of the electrolyte during this approaching process. For a liquid electrolyte in SECCM, surface tension is considered to counterbalance the gravity and electrostatic force in 2D cylindrical coordinates with axial symmetry. The deformation at equilibrium is solved under certain conditions. For a gel electrolyte, a viscoelastic gel is analysed with a simplified 1D geometry. Both equilibrium and dynamic approaching are considered. The results suggest that for both liquid and gel electrolytes, critical conditions exist for breaking the equilibrium. When the applied potential is higher or the distance is lower than the threshold, the force will not equilibrate and the electrolyte will deform until contact. The critical condition depends on the properties (surface tension for a liquid, elastic and viscous moduli for a gel) and geometry (radius of the capillary for a liquid, thickness for a gel) of the electrolyte. Prospects of further extending the work closer to real experimental scenarios, especially SGECM, are also discussed.

Electrochemical Scanning Probe Microscopy Evaluation of Li-Ion Battery Cathode Degradation through in Situ Oxygen Evolution Measurement and Interfacial Property Characterization

Degradation processes involving oxygen evolution significantly limit the performance, reversibility, and capacity of high energy density Li-ion battery (LiB) cathodes. In addition, oxygen evolution processes create hazardous conditions for LiB operation. Despite the importance of these processes, characterization of evolved O2 with sufficient spatial and temporal versatility is hampered by the complex setups required to perform electrochemical mass spectrometry, the gold standard for evaluating this process. Recently, we introduced a scanning electrochemical microscopy (SECM) approach that enables in-situ, real-time (i.e., few ms temporal resolution), chemically selective detection of O2.[1] Measurements were accomplished by positioning an SECM probe (i.e., an Au ultramicroelectrode) near operating cathode surfaces for detecting O2 via the oxygen reduction reaction (ORR). The superior signal-to-noise of this method enabled the observation of two peaks corresponding to a steady-state evolution at high voltage and a transient O2 evolution at low voltage on materials such as lithium cobalt oxide (LCO) and NMC electrodes.Here, we expand the capabilities of our technique by incorporating correlated measurements aimed at understanding how oxygen evolution profiles are related to surface electrochemical and mechanical properties. Specifically, we will focus on the use of feedback-mode SECM and the use of reactive mediators to evaluate the changes in the rates of electron transfer measured on materials undergoing O2 and after structural degradation. Furthermore, the use of electrochemical AFM allows us to measure the mechanical properties of these interfaces, in an attempt to tie the structural changes and the evolution of oxidizing species with the formation of cathode-electrolyte interfaces. Altogether, these multimodal SECM and AFM methods elucidate the manifold chemical, structural, and performance changes underpinning LiB cathode operation.[1] Mishra, A.; Sarbapalli, D.; Hossain, M.S.; Gossage, Z.T.; Li, Z.; Urban, A.; Rodríguez-López, J. Highly Sensitive Detection and Mapping of Incipient and Steady-State Oxygen Evolution from Operating Li-Ion Battery Cathodes via Scanning Electrochemical Microscopy. J. Electrochem. Soc., 2022, 169, 086501. Figure 1

Probing passivity of corroding metals using scanning electrochemical probe microscopy

AbstractPassive films are essential for the longevity of metals and alloys in corrosive environments. A great deal of research has been devoted to understanding and characterizing passive films, including their chemical composition, uniformity, thickness, porosity, and conductivity. Many characterization techniques are conducted under vacuum, which do not portray the true in‐service environments passive films will endure. Scanning electrochemical probe microscopy (SEPM) techniques have emerged as necessary tools to complement research on characterizing passive films to enable the in situ extraction of passive film parameters and monitoring of local breakdown events of compromised films. Herein, we review the current research efforts using scanning electrochemical microscopy, scanning electrochemical cell microscopy (or droplet cell measurements), and local electrochemical impedance spectroscopy techniques to advance the knowledge of local properties of passivated metals. The future use of SEPM for quantitative extraction of local film characteristics within in‐service environments (i.e., with varying pH, solution composition, and applied potential) is promising, which can be correlated to nanostructural and microstructural features of the passive film and underlying metal using complementary microscopy and spectroscopy methods. The outlook on this topic is highlighted, including exciting avenues and challenges of these methods in characterizing advanced alloy systems and protective surface films.

Electrochemical Imaging of Interfaces in Energy Storage via Scanning Probe Methods: Techniques, Applications, and Prospects.

Developing a deeper understanding of dynamic chemical, electronic, and morphological changes at interfaces is key to solving practical issues in electrochemical energy storage systems (EESSs). To unravel this complexity, an assortment of tools with distinct capabilities and spatiotemporal resolutions have been used to creatively visualize interfacial processes as they occur. This review highlights how electrochemical scanning probe techniques (ESPTs) such as electrochemical atomic force microscopy, scanning electrochemical microscopy, scanning ion conductance microscopy, and scanning electrochemical cell microscopy are uniquely positioned to address these challenges in EESSs. We describe the operating principles of ESPTs, focusing on the inspection of interfacial structure and chemical processes involved in Li-ion batteries and beyond. We discuss current examples, performance limitations, and complementary ESPTs. Finally, we discuss prospects for imaging improvements and deep learning for automation. We foresee that ESPTs will play an enabling role in advancing EESSs as we transition to renewable energies. Expected final online publication date for the Annual Review of Analytical Chemistry, Volume 16 is June 2023. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Spatially Resolved Optical Spectroscopic Measurements with Simultaneous Photoelectrochemical Mapping Using Scanning Electrochemical Probe Microscopy

A deep understanding of the properties of semiconductor films at the micro-/nanoscale level is fundamental toward designing effective photoelectrocatalysts. Here, we integrated spatially resolved optical spectroscopy (SR-OS) with scanning photoelectrochemical microscopy (SPECM) to collect UV/vis spectra and quantify photocurrents of localized sites on a nanostructured BiVO4 thin film. Direct measurement of absorbance allowed for the determination of band gap energy at each location. Absorbance and photocurrent maps were obtained and used to investigate heterogeneities on the films. Scanning electrochemical cell microscopy (SECCM) was also coupled with SR-OS to acquire quantitative photoelectrochemical data at the FTO/BiVO4 film interface, revealing higher photocurrents at the boundary regions. As a droplet-based technique, SECCM was employed to estimate the wetted area by measuring the maximum height of droplet stretch at each point, allowing for the calculation of photocurrent density. This novel approach provides an advantageous mean to correlate localized photocatalytic activities and band gap energies.

Operando Scanning Electrochemical Probe Microscopy during Electrocatalysis.

Scanning electrochemical probe microscopy (SEPM) techniques can disclose the local electrochemical reactivity of interfaces in single-entity and sub-entity studies. Operando SEPM measurements consist of using a SEPM tip to investigate the performance of electrocatalysts, while the reactivity of the interface is simultaneously modulated. This powerful combination can correlate electrochemical activity with changes in surface properties, e.g., topography and structure, as well as provide insight into reaction mechanisms. The focus of this review is to reveal the recent progress in local SEPM measurements of the catalytic activity of a surface toward the reduction and evolution of O2 and H2 and electrochemical conversion of CO2. The capabilities of SEPMs are showcased, and the possibility of coupling other techniques to SEPMs is presented. Emphasis is given to scanning electrochemical microscopy (SECM), scanning ion conductance microscopy (SICM), electrochemical scanning tunneling microscopy (EC-STM), and scanning electrochemical cell microscopy (SECCM).

Electrochemical scanning probe microscopies for artificial photosynthesis

Electrochemical scanning probe microscopies for artificial photosynthesis

Understanding molecular and electrochemical charge transfer: theory and computations.

Electron, proton, and proton-coupled electron transfer (PCET) are crucial elementary processes in chemistry, electrochemistry, and biology. We provide here a gentle overview of retrospective and currently developing theoretical formalisms of chemical, electrochemical and biological molecular charge transfer processes, with examples of how to bridge electron, proton, and PCET theory with experimental data. We offer first a theoretical minimum of molecular electron, proton, and PCET processes in homogeneous solution and at electrochemical interfaces. We illustrate next the use of the theory both for simple electron transfer processes, and for processes that involve molecular reorganization beyond the simplest harmonic approximation, with dissociative electron transfer and inclusion of all charge transfer parameters. A core example is the electrochemical reduction of the S2O82- anion. This is followed by discussion of core elements of proton and PCET processes and the electrochemical dihydrogen evolution reaction on different metal, semiconductor, and semimetal (say graphene) electrode surfaces. Other further focus is on stochastic chemical rate theory, and how this concept can rationalize highly non-traditional behaviour of charge transfer processes in mixed solvents. As a second major area we address ("long-range") chemical and electrochemical electron transfer through molecular frameworks using notions of superexchange and hopping. Single-molecule and single-entity electrochemistry are based on electrochemical scanning probe microscopies. (In operando) scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) are particularly emphasized, with theoretical notions and new molecular electrochemical phenomena in the confined tunnelling gap. Single-molecule surface structure and electron transfer dynamics are illustrated by self-assembled thiol molecular monolayers and by more complex redox target molecules. This discussion also extends single-molecule electrochemistry to bioelectrochemistry of complex redox metalloproteins and metalloenzymes. Our third major area involves computational overviews of molecular and electronic structure of the electrochemical interface, with new computational challenges. These relate to solvent dynamics in bulk and confined space (say carbon nanostructures), electrocatalysis, metallic and semiconductor nanoparticles, d-band metals, carbon nanostructures, spin catalysis and "spintronics", and "hot" electrons. Further perspectives relate to metal-organic frameworks, chiral surfaces, and spintronics.

Micro-Sized pH Sensors Based on Scanning Electrochemical Probe Microscopy.

Monitoring pH changes at the micro/nano scale is essential to gain a fundamental understanding of surface processes. Detection of local pH changes at the electrode/electrolyte interface can be achieved through the use of micro-/nano-sized pH sensors. When combined with scanning electrochemical microscopy (SECM), these sensors can provide measurements with high spatial resolution. This article reviews the state-of-the-art design and fabrication of micro-/nano-sized pH sensors, as well as their applications based on SECM. Considerations for selecting sensing probes for use in biological studies, corrosion science, in energy applications, and for environmental research are examined. Different types of pH sensitive probes are summarized and compared. Finally, future trends and emerging applications of micro-/nano-sized pH sensors are discussed.

In situ detection of multitarget impurities on contact lens by electrochemical scanning probe

Identifying multitarget impurities on contact lenses is challenging because traditional methods such as polymerase chain reaction cannot be used on the unknown target. Other sampling methods often require expensive antibodies or dyes. Therefore, this research focuses on the detection of multitarget impurities in situ on the lens surface as a more innovative and effective label-free assay using scanning electrochemical microscopy (SECM). Impurities were investigated using an electrochemical assay and an oxygen consumption assay. The electrochemical activity of BSA and the bacteria adhered to the contact lenses was explored using a FcMeOH solution. The experimental results revealed the difference in current values of the clean and protein-adsorbed contact lens samples. Furthermore, SECM can be used to detect the oxygen consumption of aerobic microbes using the oxygen reduction method. Thus, contaminated microbes can be identified without labeling in phosphate buffer saline. The mass spectra of the contact lenses were studied and the adsorption of impurities was verified. Finally, contact lens samples were investigated from various patients with ocular infection diagnosed with corneal ulcers, preseptal cellulitis, and orbital cellulitis. As a result, SECM could be a new tool for distinguishing the cleanliness of contact lenses in the future.

Scanning Electrochemical Cell Microscopy: A Tool for Nanoscopic Deposition of Light-Driven Photocatalysts

Single and multi-barrel nanopipettes and nanopipette-based scanning electrochemical probe microscopy techniques like scanning electrochemical cell microscopy (SECCM) have gained significant attention as tools for localized, maskless, three-dimensional surface modifications [1,2]. The nanometer-sized orifices of nanopipettes allow delivering molecules to solution inducing concentration-confined electrodepositions. Also, electroless nanoscale depositions like the fountain pen technique [3] can be achieved by this technique.In this study, we present the deposition of various cobaloxime-based earth-abundant Co catalysts for light-driven hydrogen evolution reaction (HER) [4]. Arrays of different cobalt(III) complexes were deposited via SECCM and investigated in respect with their HER activity using scanning electrochemical microscopy (SECM) in combination of Pd-microsensors [5] for in situ hydrogen (H2) measurements under illumination. In addition, AFM studies revealed possible degradation of the commercially available neutral benchmark complex [Co(dmgH)2(py)Cl] in these studies. First results will also be presented in respect with the deposition of nanowires via co-deposition of HER catalyst and Ruthenium photosensitizer. First spatially resolved photocatalytic studies at such nanowires, which are characterized by high surface area, will be presented. Also, the influence of the substrate will also be discussed.

Morphology and Electrochemistry Drive Corrosion of Electroless Nickel Immersion Gold Films: A Multi-Technique Analysis

Electroless nickel immersion gold (ENIG) is a common surface finish for high-reliability microelectronics circuitry due to its good solderability, corrosion resistance, layer thickness uniformity and applicability for fine pitch applications1. ENIG deposition is a multistep process in which a 3 to 6 micron (118-236 μ-in) layer of electroless nickel (i.e. Ni-P) is deposited onto the substrate material (typically copper), followed by a galvanic displacement reaction replacing the surface layer of Ni with 0.04 to 0.1 microns (1.6 to 4 μ-in) of gold (Au). Despite ENIG’s widespread use, it continues to suffer from a failure mode known as “black pad” or Ni hypercorrosion during immersion gold deposition2. A cohesive mechanistic explanation for the occurrence of Ni hypercorrosion is not yet established despite extensive study. Recent approaches have attempted to characterize in-situ the influence of bath chemistry; however, the competing influence of all variables of the ENIG process (e.g. temperature, pH, solution chemistry, volume mixing, surface morphology, etc.) make global mechanistic conclusions challenging if not impossible experimentally3. Instead, the work here aims to develop tools to assess an ENIG film of unknown origin or deposition conditions for the risk of corrosion. Therefore, this study utilizes a combination of surface characterization via x-ray photoelectron spectroscopy (XPS) depth profiling and transmission electron microscopy (TEM) imaging and electrochemical characterization via cyclic polarization (CP) and scanning vibrating electrode technique (SVET) to build a multi-technique analysis of ENIG failures.ENIG samples with identical geometries and plating requirements from two domestic vendors (A & B) were obtained. XPS with argon ion sputtering allows for comparison of atomic concentration of Ni, Au and P in ENIG films through their depth as a function of the number of sputter cycles. XPS results show that Vendor A films have a high concentration of Ni in the Au layer and a lower concentration of P near the Au-Ni interface, whereas Vendor B films have a low concentration of Ni in the Au layer and a higher concentration of P near the Au-Ni interface. This indicates a more porous morphology in Vendor A versus B films. SVET is an electrochemical scanning probe tool which allows for real-time observation of cathodic and anodic currents (in a 0.35% NaCl solution) representing existing and developing defect sites on ENIG surfaces. SVET experiments show that Vendor A and B samples exhibit preferential anodic currents on ENIG surfaces corresponding to Ni hypercorrosion defects. Focused ion beam (FIB) lift-outs from SVET samples viewed in TEM give ex-situ confirmation that SVET observations align with the real metal layer structure and chemistry as well as confirming the presence and location of corrosion products. CP curves for samples of each film in a 0.35% NaCl solution demonstrate that both Vendor A and Vendor B films exhibit effective corrosion rates above 1.0 mil per year which is on the order of bare Cu wire in the same electrolyte. Overall, a distinct difference in film morphology between Vendor A and B samples exists; however, both films exhibit substantial electrochemical activity in solution indicating corrosion susceptibility. Taken together, these results show that Ni hypercorrosion can be driven by at least two distinct mechanisms: high porosity in the Au film leading to enhanced Ni migration and reaction at the Au surface; or, P enrichment at the Au-Ni interface leading to enhanced P migration and a more electronegative surface composition. Future work will build out characterization of additional ENIG samples to establish a failure matrix for ENIG films, encompassing a wider variety of unique mechanisms. D. Goyal, T. Lane, P. Kinzie, C. Panichas, K. M. Chong, and O. Villalobos, in "52nd Electronic Components and Technology Conference 2002.(Cat. No. 02CH37345)", p. 732-739. IEEE, 2002.R. Ramanauskas, A. Selskis, J. Juodkazyte, and V. Jasulaitiene, Circuit World, (2013).A. Accogli, E. Gibertini, G. Panzeri, A. Lucotti, and L. Magagnin, Journal of The Electrochemical Society, 167 (8), 082507 (2020). SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525

Nanoscale surface modification via scanning electrochemical probe microscopy

Micro- and nanoscale surface modification using scanning probe microscopy techniques in combination with electrochemically induced surface structuring provides a maskless in situ fabrication strategy enabling deposition or etching of three-dimensional nanostructures. This current opinion article focuses on scanning electrochemical probe microscopy techniques highlighting recent progress in nanoscale 3D surface modification along with a spotlight on approaches of practical relevance.

Scanning electrochemical cell microscopy: High-resolution structure−property studies of mono- and polycrystalline electrode materials

Scanning electrochemical cell microscopy (SECCM) is a nanopipette-based scanning electrochemical probe microscopy technique that utilises a mobile droplet cell to measure and visualise electrode activity with high spatiotemporal resolution. This article spotlights the use of SECCM for studying the electrochemistry of crystalline electrode materials, ranging from well-defined monocrystals (e.g., transition metal dichalcogenides: MoS2, WS2 and WSe2) to structurally/compositionally heterogeneous polycrystals (e.g., polycrystalline Pt, Au, Pd, Cu, Zn, low carbon steel, boron-doped diamond) and covering the diverse areas of (photo)electrocatalysis, corrosion science, surface science and electroanalysis. In particular, it is emphasised how nanoscale-resolved information from SECCM is readily related to electrode structure and properties, collected at a commensurate scale with complementary, co-located microscopy/spectroscopy techniques, to allow structure–property relationships to be assigned directly and unambiguously.

Development of a Versatile, Low-Cost Electrochemical System to Study Biofilm Redox Activity at the Micron Scale

ABSTRACTSpatially resolving chemical landscapes surrounding microbial communities can provide insight into chemical interactions that dictate cellular physiology. Electrochemical techniques provide an attractive option for studying these interactions due to their robustness and high sensitivity. Unfortunately, commercial electrochemical platforms that are capable of measuring chemical activity on the micron scale are often expensive and do not easily perform multiple scanning techniques. Here, we report development of an inexpensive electrochemical system that features a combined micromanipulator and potentiostat component capable of scanning surfaces while measuring molecular concentrations or redox profiles. We validate this experimental platform for biological use with a two-species biofilm model composed of the oral bacterial pathogen Aggregatibacter actinomycetemcomitans and the oral commensal Streptococcus gordonii. We measure consumption of H2O2 by A. actinomycetemcomitans biofilms temporally and spatially, providing new insights into how A. actinomycetemcomitans responds to this S. gordonii-produced metabolite. We advance our platform to spatially measure redox activity above biofilms. Our analysis supports that redox activity surrounding biofilms is species specific, and the region immediately above an S. gordonii biofilm is highly oxidized compared to that above an A. actinomycetemcomitans biofilm. This work provides description and validation of a versatile, quantitative framework for studying bacterial redox-mediated physiology in an integrated and easily adaptable experimental platform.IMPORTANCE Scanning electrochemical probe microscopy methods can provide information of the chemical environment along a spatial surface with micron-scale resolution. These methods often require expensive instruments that perform optimized and highly sensitive niche techniques. Here, we describe a novel system that combines a micromanipulator that scans micron-sized electrodes across the surface of bacterial biofilms and a potentiostat, which performs various electrochemical techniques. This platform allows for spatial measurement of chemical gradients above live bacteria in real time, and as proof of concept, we utilize this setup to map H2O2 detoxification above an oral pathogen biofilm. We increased the versatility of this platform further by mapping redox potentials of biofilms in real time on the micron scale. Together, this system provides a technical framework for studying chemical interactions among microbes.

In Situ Detection of Multitarget Impurities on Contact Lens by Electrochemical Scanning Probe

In Situ Detection of Multitarget Impurities on Contact Lens by Electrochemical Scanning Probe