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Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold.
Electrochemical CO[Formula: see text] reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO[Formula: see text] reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO[Formula: see text] adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO[Formula: see text] adsorption at intermediate ones, and CO[Formula: see text] mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO[Formula: see text] and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport
Depleted pyrochlore antiferromagnets
I consider the class of "depleted pyrochlore" lattices of corner-sharing
triangles, made by removing spins from a pyrochlore lattice such that every
tetrahedron loses exactly one. Previously known examples are the "hyperkagome"
and "kagome staircase". I give criteria in terms of loops for whether a given
depleted lattice can order analogous to the kagome \sqrt{3} \times \sqrt{three}
state, and also show how the pseudo-dipolar correlations (due to local
constraints) generalize to even the random depleted case.Comment: 6pp IOP latex, 1 figure; Proc. "Highly Frustrated Magnetism 2008",
Sept 2008, Braunschwei
Simulation Modelling of Inequality in Cancer Service Access
This paper applies economic concepts from measuring income inequality to an
exercise in assessing spatial inequality in cancer service access in regional
areas. We propose a mathematical model for accessing chemotherapy among local
government areas (LGAs). Our model incorporates a distance factor. With a
simulation we report results for a single inequality measure: the Lorenz curve
is depicted for our illustrative data. We develop this approach in order to
move incrementally towards its application to actual data and real-world health
service regions. We seek to develop the exercises that can lead policy makers
to relevant policy information on the most useful data collections to be
collected and modeling for cancer service access in regional areas.Comment: 6 pages, 3 figure
Selective Effects of D- and L-Govadine in Preclinical Tests of Positive, Negative, and Cognitive Symptoms of Schizophrenia
There is a critical need to develop novel pharmacotherapeutics capable of addressing the positive, negative, and cognitive symptoms of schizophrenia. Building on recent studies with a racemic mixture of the synthetic tetrahydroprotoberberine, D,L-Govadine, we isolated the D- and L-stereoisomers and employed a battery of behavioral, neurochemical, and electrophysiological procedures to assess their individual therapeutic potential. Rodent models predictive of antipsychotic efficacy and those that model positive symptoms were employed and we found that L-Govadine, but not D-Govadine, improved these measures. Pretreatment with either stereoisomer during CS pre-exposure prevented the disruption of latent inhibition by amphetamine. Moreover, pretreatment with either stereoisomer also improved deficits in social interaction in the neonatal ventral hippocampal lesioned rat. Improved cognitive performance in two different prefrontal cortex-dependent tasks was observed with D-, but not L-Govadine, which strongly suggests that the D-steroisomer may be an effective cognitive enhancer. Alterations in dopamine efflux were also assessed and L-Govadine increased dopamine efflux in both the prefrontal cortex and nucleus accumbens. However, D-Govadine only increased dopamine efflux in the prefrontal cortex and not in the nucleus accumbens. Electrophysiological studies confirmed that L-Govadine is a DA-D2 antagonist, whereas D-Govadine shows no appreciable physiological effects at this receptor. Collectively these data show that L-Govadine performs well on measures predictive of antipsychotic efficacy and rodent models of positive symptoms through antagonism of DA-D2 receptors, whereas D-Govadine improves impairments in compromised memory function in delayed response tasks possibly through selective increases in DA efflux in the frontal cortex
Assessing spatial inequality in cancer service access in regional areas
This paper applies economic concepts from measuring income inequality to an exercise in assessing spatial inequality in cancer service access in regional areas. We propose a mathematical model for accessing chemotherapy among local government areas (LGAs). Our model incorporates a distance factor. With a simulation we report results for a single inequality measure: the Lorenz curve is depicted for our illustrative data. We develop this approach in order to move incrementally towards its application to actual data and real-world health service regions. We seek to develop the exercises that can lead policy makers to relevant policy information on the most useful data collections to be collected and modeling for cancer service access in regional areas
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