2,931 research outputs found
Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction
The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing ‘pseudo-single-crystal’ electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe2+/3+ couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe2+ oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale
Omnipolarity applied to equi-spaced electrode array for ventricular tachycardia substrate mapping
Aims : Bipolar electrogram (BiEGM)-based substrate maps are heavily influenced by direction of a wavefront to the mapping bipole. In this study, we evaluate high-resolution, orientation-independent peak-to-peak voltage (Vpp) maps obtained with an equi-spaced electrode array and omnipolar EGMs (OTEGMs), measure its beat-to-beat consistency, and assess its ability to delineate diseased areas within the myocardium compared against traditional BiEGMs on two orientations: along (AL) and across (AC) array splines. Methods and results: The endocardium of the left ventricle of 10 pigs (three healthy and seven infarcted) were each mapped using an Advisor™ HD grid with a research EnSite Precision™ system. Cardiac magnetic resonance images with late gadolinium enhancement were registered with electroanatomical maps and were used for gross scar delineation. Over healthy areas, OTEGM Vpp values are larger than AL bipoles by 27% and AC bipoles by 26%, and over infarcted areas OTEGM Vpp values are 23% larger than AL bipoles and 27% larger than AC bipoles (P < 0.05). Omnipolar EGM voltage maps were 37% denser than BiEGM maps. In addition, OTEGM Vpp values are more consistent than bipolar Vpps showing less beat-by-beat variation than BiEGM by 39% and 47% over both infarcted and healthy areas, respectively (P < 0.01). Omnipolar EGM better delineate infarcted areas than traditional BiEGMs from both orientations. Conclusion: An equi-spaced electrode grid when combined with omnipolar methodology yielded the largest detectable bipolar-like voltage and is void of directional influences, providing reliable voltage assessment within infarcted and non-infarcted regions of the heart.This work was funded by Abbott Laboratories, St. Paul, MN, USA.S
Structural correlations in heterogeneous electron transfer at monolayer and multilayer graphene electrodes
As a new form of carbon, graphene is attracting intense interest as an electrode material with widespread applications. In the present study, the heterogeneous electron transfer (ET) activity of graphene is investigated using scanning electrochemical cell microscopy (SECCM), which allows electrochemical currents to be mapped at high spatial resolution across a surface for correlation with the corresponding structure and properties of the graphene surface. We establish that the rate of heterogeneous ET at graphene increases systematically with the number of graphene layers, and show that the stacking in multilayers also has a subtle influence on ET kinetics. © 2012 American Chemical Society
Search for Narrow Diphoton Resonances and for gamma-gamma+W/Z Signatures in p\bar p Collisions at sqrt(s)=1.8 TeV
We present results of searches for diphoton resonances produced both
inclusively and also in association with a vector boson (W or Z) using 100
pb^{-1} of p\bar p collisions using the CDF detector. We set upper limits on
the product of cross section times branching ratio for both p\bar
p\to\gamma\gamma + X and p\bar p\to\gamma\gamma + W/Z. Comparing the inclusive
production to the expectations from heavy sgoldstinos we derive limits on the
supersymmetry-breaking scale sqrt{F} in the TeV range, depending on the
sgoldstino mass and the choice of other parameters. Also, using a NLO
prediction for the associated production of a Higgs boson with a W or Z boson,
we set an upper limit on the branching ratio for H\to\gamma\gamma. Finally, we
set a lower limit on the mass of a `bosophilic' Higgs boson (e.g. one which
couples only to \gamma, W, and Z$ bosons with standard model couplings) of 82
GeV/c^2 at 95% confidence level.Comment: 30 pages, 11 figure
Search for Chargino-Neutralino Associated Production at the Fermilab Tevatron Collider
We have searched in collisions at = 1.8 TeV for events
with three charged leptons and missing transverse energy. In the Minimal
Supersymmetric Standard Model, we expect trilepton events from
chargino-neutralino (\chione \chitwo) pair production, with subsequent decay
into leptons. We observe no candidate , ,
or events in 106 pb integrated
luminosity. We present limits on the sum of the branching ratios times cross
section for the four channels: \sigma_{\chione\chitwo}\cdot
BR(\chione\chitwo\to 3\ell+X) 81.5 \mgev\sp and
M_\chitwo > 82.2 \mgev\sp for , ~\mgev\sp and
M_\squark= M_\gluino.Comment: 9 pages and 3 figure
Measurement of the p\bar{p}\sqrt{s}$ = 1.8 TeV
We update the measurement of the top production cross section using the CDF
detector at the Fermilab Tevatron. This measurement uses decays to
the final states +jets and +jets. We search for quarks from
decays via secondary-vertex identification or the identification of
semileptonic decays of the and cascade quarks. The background to the
production is determined primarily through a Monte Carlo simulation.
However, we calibrate the simulation and evaluate its uncertainty using several
independent data samples. For a top mass of 175 , we measure
pb and pb using
the secondary vertex and the lepton tagging algorithms, respectively. Finally,
we combine these results with those from other decay channels and
obtain pb.Comment: The manuscript consists of 130 pages, 35 figures and 42 tables in
RevTex. The manuscript is submitted to Physical Review D. Fixed typo in
author lis
Search for the Supersymmetric Partner of the Top-Quark in Collisions at
We report on a search for the supersymmetric partner of the top quark (stop)
produced in events using of
collisions at recorded with the Collider Detector at
Fermilab. In the case of a light stop squark, the decay of the top quark into
stop plus the lightest supersymmetric particle (LSP) could have a significant
branching ratio. The observed events are consistent with Standard Model production and decay. Hence, we set limits on the branching ratio of
the top quark decaying into stop plus LSP, excluding branching ratios above 45%
for a LSP mass up to 40 {\rm GeV/c}.Comment: 11 pages, 4 figure
Limits on Gravitino Production and New Processes with Large Missing Transverse Energy in p-pbar Collisions at sqrt(s)=1.8 TeV
Events collected by the Collider Detector at Fermilab (CDF) with an energetic
jet plus large missing transverse energy can be used to search for physics
beyond the Standard Model. We see no deviations from the expected background
and set upper limits on the production of new processes. We consider in
addition the production of light gravitinos within the framework of the Gauge
Mediated Supersymmetry Breaking models and set a limit at 95% confidence level
on the breaking scale sqrt(F) >= 217 GeV, which excludes gravitino masses
smaller than 1.1x10^-5 eV/c^2.Comment: 13 pages, 4 figures. Submitted to Physical Review Letter
A new view of electrochemistry at highly oriented pyrolytic graphite
Major new insights on electrochemical processes at graphite electrodes are reported, following extensive investigations of two of the most studied redox couples, Fe(CN)64–/3– and Ru(NH3)63+/2+. Experiments have been carried out on five different grades of highly oriented pyrolytic graphite (HOPG) that vary in step-edge height and surface coverage. Significantly, the same electrochemical characteristic is observed on all surfaces, independent of surface quality: initial cyclic voltammetry (CV) is close to reversible on freshly cleaved surfaces (>400 measurements for Fe(CN)64–/3– and >100 for Ru(NH3)63+/2+), in marked contrast to previous studies that have found very slow electron transfer (ET) kinetics, with an interpretation that ET only occurs at step edges. Significantly, high spatial resolution electrochemical imaging with scanning electrochemical cell microscopy, on the highest quality mechanically cleaved HOPG, demonstrates definitively that the pristine basal surface supports fast ET, and that ET is not confined to step edges. However, the history of the HOPG surface strongly influences the electrochemical behavior. Thus, Fe(CN)64–/3– shows markedly diminished ET kinetics with either extended exposure of the HOPG surface to the ambient environment or repeated CV measurements. In situ atomic force microscopy (AFM) reveals that the deterioration in apparent ET kinetics is coupled with the deposition of material on the HOPG electrode, while conducting-AFM highlights that, after cleaving, the local surface conductivity of HOPG deteriorates significantly with time. These observations and new insights are not only important for graphite, but have significant implications for electrochemistry at related carbon materials such as graphene and carbon nanotubes
Measurement of Rapidity Distribution for High Mass Drell-Yan ee Pairs at CDF
We report on the first measurement of the rapidity distribution dsigma/dy
over nearly the entire kinematic region of rapidity for e^+e^- pairs in the
Z-boson region of 66116 GeV/c^2.
The data sample consists of 108 pb^{-1} of ppbar collisions at \sqrt{s}=1.8 TeV
taken by the Collider Detector at Fermilab during 1992--1995. The total cross
section in the -boson region is measured to be 252 +- 11 pb. The measured
total cross section and d\sigma/dy are compared with quantum chromodynamics
calculations in leading and higher orders.Comment: 7 pages, 3 figures. Submitted to Physical Review Letter
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