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The present shear-force constant-distance scanning electrochemical microscope regulates tip-to-substrate distance using a phase-controlled feedback mechanism that is more sensitive than the amplitude-controlled constant-distance scanning electrochemical microscopes. Phase control responds faster to frequency perturbation and presents enhance sensitivity during distance curves under constant-distance mode.

The present work uses a scanning electrochemical microscopy technique to study systems containing the membrane-bound reaction center protein (RC) from the purple photosynthetic bacteria Rhodobacter spheroides to chromatophores (spherical reorganization of cell membrane following its mechanical rupture) and liposomes (reconstituted membrane systems at lower degree of complexity). Scanning electrochemical microscopy is a useful tool to investigate redox processes involving a RC, because the effective heterogeneous rate constants for the redox reaction with different mediators can be measured. The technique is also able to provide information on the role of the outer cell membrane permeation on the kinetics of the electron-transfer processes and to obtain more insight into the nature of the species involved.

The fabrication and characterization of novel micropipet probes for use in scanning electrochemical microscopy (SECM) are described. These can be used to dispense small (pL) amounts of a solution while monitoring the electrochemical response at a substrate and at a ring electrode tip on the micropipet probe. The probes were constructed by insulating gold-coated borosilicate micropipets with electrophoretic paint and exposing a ring electrode at the tip by heat treatment. Characterization of the probes was performed using scanning electron microscopy, cyclic voltammetry, and SECM approach curve experiments. Routine construction of tips with diameters of the order of 3 [micro]m was possible using this technique. The probes exhibited stable steady-state currents and positive and negative feedback approach curves that agreed with those predicted by theory. Demonstrative SECM imaging experiments were performed using a picodispenser to continuously dispense an electroactive solution (ferrocenemethanol) to the SECM cell while the probe was located within a few micrometers of a Pt substrate surface. Oxidation of the dispensed electroactive solution was performed at the substrate, and feedback currents were measured at the probe tip by holding the gold ring at a reducing potential. This mode of tip-dispensing SECM was used to obtain images of a platinum substrate electrode while monitoring both the substrate current and the feedback current at the probe.

Hg/Pt hemispherical ultramicroelectrodes (UMEs) (25-[micro]m diameter) were prepared either by electrodeposition from a mercuric ion solution or by simple contact of the Pt disk to a hanging mercury drop electrode. The two methods produced equivalent tips. Optical inspection and electrochemical characterization of these Hg tips with methyl viologen, cobalt sepulchrate trichloride, and hexamineruthenium(III) chloride confirm the hemispherical nature of the UME. The scanning electrochemical microscopy approach curves for all three redox couples over a conductive substrate fit theoretical plots for hemispherical electrodes. The numerical solution of the diffusion equations for substrate generation--tip collection (SG-TC) transients for a finite Pt disk and Hg/Pt hemispherical UME are reported and compared to experimental results. A diffusion layer approximation is presented, and diffusion coefficients are extracted from the simulation. The SG-TC results reveal the enhanced sensitivity of hemispherical UME to radial diffusion.

The design of stable redox active liposomes is described where the organometallic electroactive pendent is covalently bound to the phospholipid headgroup through a phospholipase D (PLD)-catalyzed transphosphatidylation reaction between a choline-bearing phospholipid and a primary alcohol containing a ferrocene derivative. The functionalization of a liposome surface with the organometallic redox phospholipd has helped in studying membrane-bound electrochemical reactions, which are important for designing redox-sensitive liposome delivery systems.

The nonuniform diffusion profile to the edge of many multifunctional microelectrodes has the potential to give rise to distortions in its imaging capability, reducing the spatial accuracy of the techniques they are used in. In this work, numerical simulations are used to predict these distortions for dual-barrel electrodes used in the combined feedback/ generation-collection mode of scanning electrochemical microscopy imaging a model substrate. The sensitivity of this distortion to tip-substrate distance, electrolyte composition, and size and shape of a reactive substrate feature are discussed. Multifunctional microelectrodes have promising applications in the field of high-speed electrochemical imaging, allowing local in situ measurements of kinetics, pH, and topography to be performed consecutively rather than concurrently.1,2 The challenges associated with aligning microscopy techniques are eliminated by integrating multiple electrodes (probes) into the same sensor. A broad range of multifunctional probe geometries have been fabricated, including modified AFM tips,3-5 crescent moons,6-8 multibarrel, 9-14 and disk15,16 geometries, that are suitable for tandem techniques involving scanning electrochemical microscopy (SECM),14,17 scanning ion conductance microscopy (SICM), 2 , 6-8 ,10-13,17 scanning dropl e t methods (SDM),9,10,15,18 atomic force microscopy (AFM),1,3,4,19,20 and others.15 These techniques have been used to study substrates such as nanoparticles and nanocrystals,10,11,13,18 corroding materials,5,21 single-membrane pores,3,4,8,17 and biological samples.12,14,16,19 Despite this extensive development in multifunctional microelectrodes, the relationship between probe shape and response remains underdeveloped for multifunctional microelectrodes outside of discussions of probe size. [ABSTRACT FROM AUTHOR]

The article offers information on the recent trends in scanning probe techniques that are useful in understanding magnesium alloy corrosion.

Scanning electrochemical cell microscopy is becoming the tool of choice for the investigation of localized metal corrosion. Typically, potentiodynamic polarization measurements in scanning electrochemical cell microscopy are performed at high potential scan rates. However, Tafel extrapolation applied to high-scan-rate potentiodynamic polarization curves would yield inaccurate corrosion kinetics due to the interference of double-layer charging current or mass transport of species in the metal oxide. Instead, the high field model was used to simulate the potentiodynamic polarization curves of pure aluminum at 25, 50, 100, and 200 mV/s in neutral and acidic phosphate solutions, thus enabling quantitative analysis of local corrosion kinetics by fitting the potentiodynamic polarization curve.

Efficient delivery of therapeutic compounds to their sites of action has been a ubiquitous concern throughout the history of human medicine. The tumor microenvironment offers a variety of endogenous stimuli that may be exploited by a responsive nanocarrier, including heterogeneities in redox potential. In the early stages of the design of such responsive delivery systems, it is necessary to develop a comprehensive understanding of the biophysical mechanism by which the stimulus response occurs, as well as how the response may change from the inclusion of cargo compounds. We describe the optimization of lipid compositions for liposomes containing synthetic ferrocene-appended lipids to achieve highly efficient loading of doxorubicin via an ethylenediaminetetraacetic acid (EDTA) gradient. Liposomes containing ferrocenylated phospholipid are shown to be unstable to the loading conditions, while those including a ferrocenylated alkylammonium amphiphile obtain a near-quantitative loading efficiency. Calorimetric studies demonstrate that this instability is the consequence of the relative degree of lipid hydrolysis that occurs under the acidic loading conditions. Drug-loaded liposomes of the optimized composition are studied by cryo-TEM; the presence of doxorubicin aggregates is observed inside vesicles, and doxorubicin release, as well as the changes in membrane structure resulting from oxidant treatment, is also observed by cryogenic transmission electron microscopy (cryo-TEM). These results further demonstrate the potential of ferrocene lipids in the design of redox-responsive nanocarriers and begin to explore their possible role as probes of membrane dynamics.

Quantitative scanning micropipette contact method measurements are subject to the deleterious effects of reference electrode interference. The commonly used Ag/AgCl wire quasi-reference counter electrode in the miniaturized electrochemical cell of the scanning micropipette contact method was found to leak Ag + into the electrolyte solution. The reduction of these Ag + species at the working electrode surface generates a faradaic current, which significantly affects the low magnitude currents inherently measured in the scanning micropipette contact method. We demonstrate that, during the microscopic corrosion investigation of the AA7075-T73 alloy using the oil-immersed scanning micropipette contact method, the cathodic current was increased by the Ag + reduction, resulting in positive shifts of corrosion potentials. The use of a leak-free Ag/AgCl electrode or an extended distance between the Ag/AgCl wire and micropipette tip droplet eliminated the Ag + contamination, making it possible to measure accurate corrosion potentials during the oil-immersed scanning micropipette contact method measurements.

To achieve super-resolution scanning electrochemical microscopy (SECM), we must overcome the theoretical limitation associated with noncontact electrochemical imaging of surface-generated species. This is the requirement for mass transfer to the electrode, which gives rise to the diffusional broadening of surface features. In this work, a procedure is developed for overcoming this limitation and thus generating "super-resolved" images using point spread function (PSF)-based deconvolution, where the point conductor plays the same role as the point emitter in optical imaging. In contrast to previous efforts in SECM towards this goal, our method uses a finite element model to generate a pair of corresponding blurred and sharp images for PSF estimation, avoiding the need to perform parameter optimization for effective deconvolution. It can therefore be used for retroactive data treatment and an enhanced understanding of the structure-property relationships that SECM provides.

We report a redox-responsive liposomal system capable of oxidatively triggered disassembly. We describe the synthesis, electrochemical characterization, and incorporation into vesicles of an alternative redox lipid with significantly improved synthetic efficiency and scalability compared to a ferrocene-appended phospholipid previously employed by our group in giant vesicles. The redox-triggered disassembly of both redox lipids is examined in nanosized liposomes as well as the influence of cholesterol mole fraction on liposome disassembly and suitability of various chemical oxidants for  in vitro disassembly experiments. Electronic structure density functional theory calculations of membrane-embedded ferrocenes are provided to characterize the role of charge redistribution in the initial stages of the disassembly process.

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

The site-specific incorporation of transition-metal complexes within DNA duplexes, followed by their immobilization on a gold surface, was studied by electrochemistry to characterize their ability to mediate charge. Cyclic voltammetry, square-wave voltammetry, and control experiments were carried out on fully matched and mismatched DNA strands that are mono- or bis-labeled with transition-metal complexes. These experiments are all consistent with the ability of the metal centers to act as a redox probe that is well coupled to the DNA π-stack, allowing DNA-mediated charge transport.

The electrochemical properties and electrogenerated chemiluminescence (ECL) of an Ir(ppy)2(bpy)(+)-containing ROMP monomer, block copolymer (containing Ir(ppy)2(bpy)(+) complexes, PEG chains, and butyl moieties), and self-assembled micelles were investigated. Following polymerization of the iridium complex, we observed multiple oxidation peaks for the block copolymer in cyclic voltammograms (CV) and differential pulse voltammograms (DPV), suggesting the presence of multiple environments for the iridium complexes along the polymer backbone. The ECL signals from monomer 1 and polymer 2 were reproducible over continuous CV cycles and stable over prolonged potential biases, demonstrating their robustness toward ECL-based detection. Comparison of the ECL signal of the block copolymer, containing multiple iridium complexes attached to the backbone, and the monomeric complex showed enhanced signals for the polymer. In fact, formation and reopening of the self-assembled micelles allowed recovery of the polymer and near complete retention of its original ECL intensity.