An official website of the United States government
Electrochemical reactions at nanoscale structures possess unique characteristics, e.g. fast mass transport, high signal-to-noise ratio at low concentration, and insignificant ohmic losses even at low electrolyte concentrations. These properties motivate the fabrication of high density, laterally ordered arrays of nanopores, embedding vertically stacked metal–insulator–metal electrode structures and exhibiting precisely controlled pore size and interpore spacing for use in redox cycling. These nanoscale recessed ring-disk electrode (RRDE) arrays exhibit current amplification factors, AF RC , as large as 55-fold with Ru(NH 3 ) 6 2/3+ , indicative of capture efficiencies at the top and bottom electrodes, Φ t,b , exceeding 99%. Finite element simulations performed to investigate the concentration distribution of redox species and to assess operating characteristics are in excellent agreement with experiment. AF RC increases as the pore diameter, at constant pore spacing, increases in the range 200–500 nm and as the pore spacing, at constant pore diameter, decreases in the range 1000–460 nm. Optimized nanoscale RRDE arrays exhibit a linear current response with concentration ranging from 0.1 μM to 10 mM and a small capacitive current with scan rate up to 100 V s −1 . At the lowest concentrations, the average pore occupancy is 〈 n 〉 ∼ 0.13 molecule establishing productive electrochemical signals at occupancies at and below the single molecule level in these nanoscale RRDE arrays.
more »
« less
Average collision velocity of single yeast cells during electrochemically induced impacts
We recorded current-time (i-t) profiles for oxidizing ferrocyanide (FCN) while spherical yeast cells of radius (rc ≈ 2 μm) collided with disk ultramicroelectrodes (UMEs) of increasing radius (re ≈ 12-45 μm). Collision signals appear as minority steps and majority blips of decreased current overlayed on the i-t baseline when cells block ferrocyanide flux (JFCN). We assigned steps to adsorption events and blips to bouncing collisions or contactless passages. Yeast cells exhibit impact signals of long duration (Δt ≈ 15-40 s) likely due to sedimentation. We assume cells travel a threshold distance (T) to generate collision signals of duration Δt. Thus, T represents a distance from the UME surface, at which cell perturbations on JFCN blend in with the UME noise level. To determine T, we simulated the UME current, while placing the cell at increasing distal points from the UME surface until matching the bare UME current. T-Values at 90°, 45°, and 0° from the UME edge and normal to the center were determined to map out T-regions in different experimental conditions. We estimated average collision velocities using the formula T/Δt, and mimicked cells entering and leaving T-regions at the same angle. Despite such oversimplification, our analysis yields average velocities compatible with rigorous transport models and matches experimental current steps and blips. We propose that single-cells encode collision dynamics into i-t signals only when cells move inside the sensitive T-region, because outside, perturbations of JFCN fall within the noise level set by JFCN and rc/re (experimentally established). If true, this notion will enable selecting conditions to maximize sensitivity in stochastic blocking electrochemistry. We also exploited the long Δt recorded here for yeast cells, which was undetectable for the fast microbeads used in early pioneering work. Because Δt depends on transport, it provides another analytical parameter besides current for characterizing slow-moving cells like yeast..
more »
« less
- Award ID(s):
- 1942395
- PAR ID:
- 10561003
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- The Analyst
- Volume:
- 149
- Issue:
- 11
- ISSN:
- 0003-2654
- Page Range / eLocation ID:
- 3214 to 3223
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Single-particle electrochemistry has become an important area of research with the potential to determine the rules of electrochemical reactivity at the nanoscale. These techniques involve addressing one entity at the time, as opposed to the conventional electrochemical experiment where a large number of molecules interact with an electrode surface. These experiments have been made feasible through the utilization of ultramicroelectrode (UMEs), i.e., electrodes with at least one dimension, e.g., diameter of 30 μm or less. This paper provides a theoretical and practical introduction to single entity electrochemistry (SEE), with emphasis on collision experiments between suspended NPs and UMEs to introduce concepts and techniques that are used in several SEE experimental modes. We discuss the intrinsically small currents, below 1 nA, that result from the electroactive area of single entities in the nanometer scale. Individual nanoparticles can be detected using the difference in electrochemical reactivity between a substrate and a nanoparticle (NP). These experiments show steady-state behavior of single NPs that result in discrete current changes or steps. Likewise, the NP can have transient interactions with the substrate electrode that result in current blips. We review the effect of diffusion, the main mass transport process that limits NP/electrode interactions. Also, we pointed out the implications of aggregation and tunneling in the experiments. Finally, we provid a perspective on the possible applications of single-element electrochemistry of electrocatalyst.more » « less
-
ABSTRACT We introduce a new model for understanding AGN continuum variability. We start from a Shakura–Sunyaev thin accretion disc with a steady-state radial temperature profile T(R) and assume that the variable flux is due to axisymmetric temperature perturbations δT(R, t). After linearizing the equations, we fit UV–optical AGN light curves to determine δT(R, t) for a sample of seven AGNs. We see a diversity of |δT/T| ∼ 0.1 fluctuation patterns which are not dominated by outgoing waves travelling at the speed of light as expected for the ‘lamppost’ model used to interpret disc reverberation mapping studies. Rather, the most common pattern resembles slow (v ≪ c) ingoing waves. An explanation for our findings is that these ingoing waves trigger central temperature fluctuations that act as a lamppost, producing lower amplitude temperature fluctuations moving outwards at the speed of light. The light curves are dominated by the lamppost signal – even though the temperature fluctuations are dominated by other structures with similar variability time-scales – because the discs exponentially smooth the contributions from the slower moving (v ≪ c) fluctuations to the observed light curves. This leads to light curves that closely resemble the expectations for a lamppost model but with the slow variability time-scales of the ingoing waves. This also implies that longer time-scale variability signals will increasingly diverge from lamppost models because the smoothing of slower moving waves steadily decreases as their period or spatial wavelength increases.more » « less
-
Temperature dependence studies of electrochemical parameters provide insight into electron transfer processes. In cases where adding excess electrolyte causes experimental complications, e.g., colloidal systems, organic or biological samples, it is preferable to deal with the high resistivity of the medium. We validate the use of unsupported and weakly-supported solutions in thermoelectrochemical experiments. The temperature dependence of the diffusion coefficient allows calibration of the steady-state current to measure changes when a continuous-wave (CW) ultraviolet laser,λ= 325 nm, illuminates an ultramicroelectrode (UME) from the front. Calibrating the steady-state current ratios, before and after heating with a thermostatic bath, allows temperature measurements within an accuracy of 0.6 K. The solutions are without supporting electrolytes in methanol, a volatile solvent, and we use a model that accurately describes the viscosity and temperature dependence of the solvent. We calculated the temperature and derived an equation to estimate the error in the temperature measurement. A numeric method yields satisfactory results, considering the changes for both diffusion coefficients and viscosity explicitly, and predicts the thermostatic temperature bath, agreeing with the theoretical model’s error. In unsupported solutions, the ferrocene diffusion coefficient and the iodide apparent diffusion coefficient follow the expected increase with temperature. Under CW laser illumination, the UME temperature increase is: ΔT = 4 ± 1 K.more » « less
-
Metallosphaera sedulais a thermoacidophilic archaeon that obtains all of its energy for growth from aerobic respiration and oxidative phosphorylation at the expense of selected organic and inorganic sources of electrons. Initial velocities for the oxidation of soluble ferrous ions by intact cells at 60 °C and pH 1.5 were determined using an integrating cavity absorption meter that permitted accurate absorbance measurements to quantify the increase in soluble ferric iron in the presence of turbid suspensions of the live organisms.M. sedulathat was cultured on yeast extract either in the absence or the presence of 20 mM soluble ferrous iron exhibited turnover numbers for soluble iron oxidation of 304 ± 26 and 333 ± 31 attamoles/cell/min, respectively. These functional data were consistent with the transcriptomic evidence presented by others, that the proteins presumably responsible for aerobic respiration on soluble iron are expressed constitutively inM. sedula. Intact cells ofM. sedulawere characterized by electrical impedance, laser light diffraction, and transmission electron microscopic measurements. All three types of measurements were consistent with the surprising observation that cells cultured on yeast extract in the presence of soluble iron bifurcated into approximately equal numbers of coccoidal cells of two sizes, smaller cells with an average diameter of 0.6 μm and larger cells with an average diameter of 1.35 μm. Cells cultured on the same concentration of yeast extract but in the absence of soluble iron comprised a single cell size with an intermediate average diameter of 1.06 μm. This unexpected bifurcation of a clonal cell population into two demonstrably different sizes when the extracellular nutrient environment changes has not previously been reported forM. sedula, or any other single-celled archaeon or eubacterium.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D4AN00134F
