Effect of Structure on the Spin Switching and Magnetic Bistability of Solid-State Aryl Dicyanomethyl Monoradicals and Diradicals

Stable organic radicals with switchable spin states have applications in medicine, biology, and material science. An emerging class of such spin-switchable radicals is based on dicyanomethyl radicals, which are typically thermally and air-stable species that form weakly bonded (closed-shell singlet) dimers at a lower temperature that rupture into electron paramagnetic resonance-active diradicals at a higher temperature. However, thus far, the study of these dicyanomethyl radicals has focused on their solution-phase behavior. An understanding of how chemical structure affects the solid-state spin switching behavior for these radicals is unknown. Here, we examine the solid-state spin crossover behavior of 6 monoradicals and 10 tethered diradicals and demonstrate that these species also undergo spin switching in the solid state. We find that the susceptibility for solid-state spin switching for the intermolecular dimers is weakly correlated to the solution-phase Gibbs free energies of dimerization, but no apparent correlations are seen between the solution-state free energies for the intramolecular dimerization and the solid-state behavior. Furthermore, intramolecular diradical dimers have greatly enhanced temperature-responsive behavior compared to their intermolecular counterparts. Crystalline and amorphous powders of the same radicals feature similar spin switching behavior, but the crystalline materials have slower bond-rupture kinetics at higher temperatures, suggesting that solid-state packing effects are an important kinetic consideration. An interesting feature of these systems is that, upon cooling down to room temperature after heating, some radicals remain trapped in the solids, indicating magnetic bistability, while others partially or fully return to the diamagnetic dimers. This work provides insights into how chemical structure affects spin crossover in the solid state for this new class of air-stable radicals, the knowledge of importance for the construction of dynamically responsive solid-state materials, and organic spin crossover polymers

Dietary nitrate-induced increases in human muscle power: High versus low responders

Maximal neuromuscular power is an important determinant of athletic performance and also quality of life, independence, and perhaps even mortality in patient populations. We have shown that dietary nitrate (NO3- ), a source of nitric oxide (NO), improves muscle power in some, but not all, subjects. The present investigation was designed to identify factors contributing to this interindividual variability. Healthy men (n = 13) and women (n = 7) 22-79 year of age and weighing 52.1-114.9 kg were studied using a randomized, double-blind, placebo-controlled, crossover design. Subjects were tested 2 h after ingesting beetroot juice (BRJ) either containing or devoid of 12.3 ± 0.8 mmol of NO3- . Plasma NO3- and nitrite (NO2- ) were measured as indicators of NO bioavailability and maximal knee extensor speed (Vmax ), power (Pmax ), and fatigability were determined via isokinetic dynamometry. On average, dietary NO3- increased (P < 0.05) Pmax by 4.4 ± 8.1%. Individual changes, however, ranged from -9.6 to +26.8%. This interindividual variability was not significantly correlated with age, body mass (inverse of NO3- dose per kg), body mass index (surrogate for body composition) or placebo trial Vmax or fatigue index (in vivo indicators of muscle fiber type distribution). In contrast, the relative increase in Pmax was significantly correlated (r = 0.60; P < 0.01) with the relative increase in plasma NO2- concentration. In multivariable analysis female sex also tended (P = 0.08) to be associated with a greater increase in Pmax. We conclude that the magnitude of the dietary NO3- -induced increase in muscle power is dependent upon the magnitude of the resulting increase in plasma NO2- and possibly female sex

Spatial-Temporal Modeling of Neighborhood Sociodemographic Characteristics and Food Stores

The literature on food stores, neighborhood poverty, and race/ethnicity is mixed and lacks methods of accounting for complex spatial and temporal clustering of food resources. We used quarterly data on supermarket and convenience store locations from Nielsen TDLinx (Nielsen Holdings N.V., New York, New York) spanning 7 years (2006–2012) and census tract-based neighborhood sociodemographic data from the American Community Survey (2006–2010) to assess associations between neighborhood sociodemographic characteristics and food store distributions in the Metropolitan Statistical Areas (MSAs) of 4 US cities (Birmingham, Alabama; Chicago, Illinois; Minneapolis, Minnesota; and San Francisco, California). We fitted a space-time Poisson regression model that accounted for the complex spatial-temporal correlation structure of store locations by introducing space-time random effects in an intrinsic conditionally autoregressive model within a Bayesian framework. After accounting for census tract–level area, population, their interaction, and spatial and temporal variability, census tract poverty was significantly and positively associated with increasing expected numbers of supermarkets among tracts in all 4 MSAs. A similar positive association was observed for convenience stores in Birmingham, Minneapolis, and San Francisco; in Chicago, a positive association was observed only for predominantly white and predominantly black tracts. Our findings suggest a positive association between greater numbers of food stores and higher neighborhood poverty, with implications for policy approaches related to food store access by neighborhood poverty

Dietary Nitrate Increases VO2peak and Performance but Does Not Alter Ventilation or Efficiency in Patients With Heart Failure With Reduced Ejection Fraction

Background Patients with heart failure with reduced ejection fraction (HFrEF) exhibit lower efficiency, dyspnea, and diminished peak oxygen uptake (VO2peak) during exercise. Dietary nitrate (NO3−), a source of nitric oxide (NO), has improved these measures in some studies of other populations. We determined the effects of acute NO3− ingestion on exercise responses in 8 patients with HFrEF using a randomized, double-blind, placebo-controlled, crossover design. Methods and Results Plasma NO3−, nitrite (NO2−), and breath NO were measured at multiple time points and respiratory gas exchange was determined during exercise after ingestion of beetroot juice containing or devoid of 11.2 mmol of NO3−. NO3− intake increased (P < .05–0.001) plasma NO3− and NO2− and breath NO by 1469 ± 245%, 105 ± 34%, and 60 ± 18%, respectively. Efficiency and ventilation during exercise were unchanged. However, NO3− ingestion increased (P < .05) VO2peak by 8 ± 2% (ie, from 21.4 ± 2.1 to 23.0 ± 2.3 mL.min−1.kg−1). Time to fatigue improved (P < .05) by 7 ± 3 % (ie, from 582 ± 84 to 612 ± 81 seconds). Conclusions Acute dietary NO3− intake increases VO2peak and performance in patients with HFrEF. These data, in conjunction with our recent data demonstrating that dietary NO3− also improves muscle contractile function, suggest that dietary NO3− supplementation may be a valuable means of enhancing exercise capacity in this population

Explanatory Style as a Risk Factor for Traumatic Mishaps

Six studies investigated a possible link between hopeless explanatory style—that is, the habitual explanation of bad events with stable and global causes—and risk for traumatic injuries. In samples of college students, dancers, athletes, and trauma patients (total n = 2274), stable and global explanations for bad events correlated with the occurrence of mishaps. The link appeared to be mediated in part by a preference for potentially hazardous settings and activities in response to negative moods associated with hopelessness. Taken together, these findings suggest that catastrophizing individuals may be motivated to escape negative moods by preferring exciting but risky courses of action.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/44339/1/10608_2004_Article_363208.pd

Revealing important nocturnal and day-to-day variations in fire smoke emissions through a multiplatform inversion

We couple airborne, ground-based, and satellite observations; conduct regional simulations; and develop and apply an inversion technique to constrain hourly smoke emissions from the Rim Fire, the third largest observed in California, USA. Emissions constrainedwithmultiplatform data show notable nocturnal enhancements (sometimes over a factor of 20), correlate better with daily burned area data, and are a factor of 2–4 higher than a priori estimates, highlighting the need for improved characterization of diurnal profiles and day-to-day variability when modeling extreme fires. Constraining only with satellite data results in smaller enhancements mainly due to missing retrievals near the emissions source, suggesting that top-down emission estimates for these events could be underestimated and a multi-platform approach is required to resolve them. Predictions driven by emissions constrained with multi-platform data present significant variations in downwind air quality and in aerosol feedback on meteorology, emphasizing the need for improved emissions estimates during exceptional events