Characterizing heterogeneous dynamics at hydrated electrode surfaces

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this adlayer dynamic heterogeneity responds asymmetrically to applied voltage.Comment: 6 page, 4 figure

Solvation at Aqueous Metal Electrodes

We present a study of the solvation properties of model aqueous electrode interfaces. The exposed electrodes we study strongly bind water and have closed packed crystalline surfaces, which template an ordered water adlayer adjacent to the interface. We find that these ordered water structures facilitate collective responses in the presence of solutes that are correlated over large lengthscales and across long timescales. Specifically, we show that the liquid water adjacent to the ordered adlayers forms a soft, liquid-vapor-like interface with concomitant manifestations of hydrophobicity. Temporal defects in the adlayer configurations create a dynamic heterogeneity in the degree to which different regions of the interface attract hydrophobic species. The structure and heterogeneous dynamics of the adlayer defects depend upon the geometry of the underlying ordered metal surface. For both 100 and 111 surfaces, the dynamical heterogeneity relaxes on times longer than nanoseconds. Along with analyzing time scales associated with these effects, we highlight implications for electrolysis and the particular catalytic efficiency of platinum.Comment: 9 pages, 8 figure

Better estimates from binned income data: Interpolated CDFs and mean-matching

Researchers often estimate income statistics from summaries that report the number of incomes in bins such as \$0-10,000, \$10,001-20,000,...,\$200,000+. Some analysts assign incomes to bin midpoints, but this treats income as discrete. Other analysts fit a continuous parametric distribution, but the distribution may not fit well. We fit nonparametric continuous distributions that reproduce the bin counts perfectly by interpolating the cumulative distribution function (CDF). We also show how both midpoints and interpolated CDFs can be constrained to reproduce the mean of income when it is known. We compare the methods' accuracy in estimating the Gini coefficients of all 3,221 US counties. Fitting parametric distributions is very slow. Fitting interpolated CDFs is much faster and slightly more accurate. Both interpolated CDFs and midpoints give dramatically better estimates if constrained to match a known mean. We have implemented interpolated CDFs in the binsmooth package for R. We have implemented the midpoint method in the rpme command for Stata. Both implementations can be constrained to match a known mean.Comment: 20 pages (including Appendix), 3 tables, 2 figures (+2 in Appendix

The Nonprofit Quarterly Study on Nonprofit and Philanthropic Infrastructure

Examines trends in the nonprofit sector's support network and financing system and their capacity to address the impact of the financial crisis on small and midsize nonprofits, share organizational survival strategies, and connect them to resources

Mortality from infectious pneumonia in metal workers: a comparison with deaths from asthma in occupations exposed to respiratory sensitizers

Introduction: national analyses of mortality in England and Wales have repeatedly shown excess deaths from pneumonia in welders. During 1979-1990 the excess was attributable largely to deaths from lobar pneumonia and pneumonias other than bronchopneumonia, limited to working-aged men, and apparent in other metal fume-exposed occupations. We assessed findings for 1991-2000 and compared the mortality pattern with that from asthma in occupations exposed to known respiratory sensitizers.Methods: the Office of National Statistics supplied data on deaths by underlying cause among men aged 16-74 years in England and Wales during 1991-2000, including age and last held occupation. We abstracted data on pneumonia for occupations with exposure to metal fume and on asthma for occupations commonly reported to surveillance schemes as at risk of occupational asthma. We estimated expected numbers of deaths by applying age-specific proportions of deaths by cause in the population to the total deaths by age in each occupational group. Observed and expected numbers were compared for each cause of death.Results: among working-aged men in metal fume-exposed occupations we found excesses of mortality from pneumococcal and lobar pneumonia (54 deaths vs. 27.3 expected) and from pneumonias other than bronchopneumonia (71 vs. 52.4), but no excess from these causes at older ages, or from bronchopneumonia at any age. The attributable mortality from metal fume (45.3 excess deaths) compared with an estimated 62.6 deaths from occupational asthma.Conclusion: exposure to metal fume is a material cause of occupational mortality. The hazard deserves far more attention than it presently receive

Enhanced recovery after surgery

Enhanced Recovery or Fast Track Recovery after Surgery protocols (ERAS) have significantly changed perioperative care following colorectal surgery and are promoted as reducing the stress response to surgery. The present systematic review aimed to examine the impact on the magnitude of the systemic inflammatory response (SIR) for each ERAS component following colorectal surgery using objective markers such as C-reactive protein (CRP) and interleukin-6 (IL-6). A literature search was performed of the US National Library of Medicine (MEDLINE), EMBASE, PubMed, and the Cochrane Database of Systematic Reviews using appropriate keywords and subject headings to February 2015. Included studies had to assess the impact of the selected ERAS component on the SIR using either CRP or IL-6. Nineteen studies, including 1898 patients, were included. Fourteen studies (1246 patients) examined the impact of laparoscopic surgery on the postoperative markers of SIR. Ten of these studies (1040 patients) reported that laparoscopic surgery reduced postoperative CRP. One study (53 patients) reported reduced postoperative CRP using opioid-minimising analgesia. One study (142 patients) reported no change in postoperative CRP following preoperative carbohydrate loading. Two studies (108 patients) reported conflicting results with respect to the impact of goal-directed fluid therapy on postoperative IL-6. No studies examined the effect of other ERAS components, including mechanical bowel preparation, antibiotic prophylaxis, thromboprophylaxis, and avoidance of nasogastric tubes and peritoneal drains on markers of the postoperative SIR following colorectal surgery. The present systematic review shows that, with the exception of laparoscopic surgery, objective evidence of the effect of individual components of ERAS protocols in reducing the stress response following colorectal surgery is limited

Charge fluctuations in nano-scale capacitors

The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers in particular an efficient, accurate and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes, and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid