SFG Study of the Potential-Dependent Adsorption of the p-Toluenesulfonate Anion at an Activated Carbon/Propylene Carbonate Interface

Sum frequency generation spectroscopy has been used to characterize the potential-dependent adsorption of the p-toluenesulfonate anion at the activated carbon/propylene carbonate interface of the commercial carbon YP50F. Spectra recorded from the interface between YP50F and a 1 M tetraethylammonium p-toluenesulfonate in propylene carbonate solution showed no ordered anion adsorption without an applied potential. In contrast, there is clear evidence of increasingly ordered anion adsorption with applied potential. Furthermore, there is evidence of hysteresis such that the anion remains adsorbed when the applied potential was decreased back to 0 V. Significant reversal of polarity was required before the anion signal was lost. Changes to the propylene carbonate solvent peaks during the electrochemical cycle were also observed. The data indicate that the positive electrode charges either via a counterion adsorption mechanism or via an ion-exchange mechanism.E.K.H. acknowledges the European Research Council ERC Grant ERC-2009-AdG-247411 for funding

New Insights into the Structure of Nanoporous Carbons from NMR, Raman, and Pair Distribution Function Analysis

The structural characterization of nanoporous carbons is a challenging task as they generally lack long-range order and can exhibit diverse local structures. Such characterization represents an important step toward understanding and improving the properties and functionality of porous carbons, yet few experimental techniques have been developed for this purpose. Here we demonstrate the application of nuclear magnetic resonance (NMR) spectroscopy and pair distribution function (PDF) analysis as new tools to probe the local structures of porous carbons, alongside more conventional Raman spectroscopy. Together, the PDFs and the Raman spectra allow the local chemical bonding to be probed, with the bonding becoming more ordered for carbide-derived carbons (CDCs) synthesized at higher temperatures. The ring currents induced in the NMR experiment (and thus the observed NMR chemical shifts for adsorbed species) are strongly dependent on the size of the aromatic carbon domains. We exploit this property and use computer simulations to show that the carbon domain size increases with the temperature used in the carbon synthesis. The techniques developed here are applicable to a wide range of porous carbons and offer new insights into the structures of CDCs (conventional and vacuum-annealed) and coconut shell-derived activated carbons.A.C.F., J.M.G., C.M., P.K.A, E.K.H., and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (via the Supergen consortium, J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. C.M. and P.K.A. acknowledge the School of the Physical Sciences of the University of Cambridge for funding through an Oppenheimer Research Fellowship. P.K.A. acknowledges a Junior Research Fellowship from Gonville and Caius College, Cambridge. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. M.A., M.Z., and V.P. acknowledge funding from the German Federal Ministry for Research and Education (BMBF) in support of the nanoEES3D project (Award Number 03EK3013) as part of the strategic funding initiative energy storage framework and kindly thank Prof. Arzt (INM) for his continuing support. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Daan Frenkel for his contributions to this work and Boris Dyatkin for comments on the manuscript.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/acs.chemmater.5b0321

Different skeletal effects of the peroxisome proliferator activated receptor (PPAR)α agonist fenofibrate and the PPARγ agonist pioglitazone

<p>Abstract</p> <p>Background</p> <p>All the peroxisome proliferator activated receptors (PPARs) are found to be expressed in bone cells. The PPARγ agonist rosiglitazone has been shown to decrease bone mass in mice and thiazolidinediones (TZDs) have recently been found to increase bone loss and fracture risk in humans treated for type 2 diabetes mellitus. The aim of the study was to examine the effect of the PPARα agonist fenofibrate (FENO) and the PPARγ agonist pioglitazone (PIO) on bone in intact female rats.</p> <p>Methods</p> <p>Rats were given methylcellulose (vehicle), fenofibrate or pioglitazone (35 mg/kg body weight/day) by gavage for 4 months. BMC, BMD, and body composition were measured by DXA. Histomorphometry and biomechanical testing of excised femurs were performed. Effects of the compounds on bone cells were studied.</p> <p>Results</p> <p>The FENO group had higher femoral BMD and smaller medullary area at the distal femur; while trabecular bone volume was similar to controls. Whole body BMD, BMC, and trabecular bone volume were lower, while medullary area was increased in PIO rats compared to controls. Ultimate bending moment and energy absorption of the femoral shafts were reduced in the PIO group, while similar to controls in the FENO group. Plasma osteocalcin was higher in the FENO group than in the other groups. FENO stimulated proliferation and differentiation of, and OPG release from, the preosteoblast cell line MC3T3-E1.</p> <p>Conclusion</p> <p>We show opposite skeletal effects of PPARα and γ agonists in intact female rats. FENO resulted in significantly higher femoral BMD and lower medullary area, while PIO induced bone loss and impairment of the mechanical strength. This represents a novel effect of PPARα activation.</p

Cognitive, Behavioral and Goal Adjustment Coping and Depressive Symptoms in Young People with Diabetes: A Search for Intervention Targets for Coping Skills Training

The aim of the present study was to find relevant coping factors for the development of psychological intervention programs for young people with Type 1 (T1) diabetes. A wide range of coping techniques was studied, including cognitive coping, behavioral coping and goal adjustment coping. A total of 78 young people with T1 diabetes participated. They were contacted through a social networking website, several Internet sites, and flyers. A wide range of coping techniques appeared to be related to depressive symptoms. Especially the cognitive coping strategies self-blame, rumination, refocus positive, and other-blame, together with goal adjustment coping, were of importance. A large proportion of the variance of depressive symptoms could be explained (65 %). These findings suggest that these specific coping strategies should be part of coping skills trainings for young people with T1 diabetes

Prdm9, a Major Determinant of Meiotic Recombination Hotspots, Is Not Functional in Dogs and Their Wild Relatives, Wolves and Coyotes

Meiotic recombination is a fundamental process needed for the correct segregation of chromosomes during meiosis in sexually reproducing organisms. In humans, 80% of crossovers are estimated to occur at specific areas of the genome called recombination hotspots. Recently, a protein called PRDM9 was identified as a major player in determining the location of genome-wide meiotic recombination hotspots in humans and mice. The origin of this protein seems to be ancient in evolutionary time, as reflected by its fairly conserved structure in lineages that diverged over 700 million years ago. Despite its important role, there are many animal groups in which Prdm9 is absent (e.g. birds, reptiles, amphibians, diptera) and it has been suggested to have disruptive mutations and thus to be a pseudogene in dogs. Because of the dog's history through domestication and artificial selection, we wanted to confirm the presence of a disrupted Prdm9 gene in dogs and determine whether this was exclusive of this species or whether it also occurred in its wild ancestor, the wolf, and in a close relative, the coyote. We sequenced the region in the dog genome that aligned to the last exon of the human Prdm9, containing the entire zinc finger domain, in 4 dogs, 17 wolves and 2 coyotes. Our results show that the three canid species possess mutations that likely make this gene non functional. Because these mutations are shared across the three species, they must have appeared prior to the split of the wolf and the coyote, millions of years ago, and are not related to domestication. In addition, our results suggest that in these three canid species recombination does not occur at hotspots or hotspot location is controlled through a mechanism yet to be determined

Splitting and blaming: The psychic life of neoliberal executive women

The aim of the article is to explore the psychic life of executive women under neoliberalism using psychosocial approaches. The article shows how, despite enduring unfair treatment and access to opportunities, many executive women remain emotionally invested in upholding the neoliberal ideal that if one perseveres, one shall be successful, regardless of gender. Drawing on psychosocial approaches, we explore how the accounts given by some executive women of repudiation, as denying gender inequality, and individualization, as subjects completely agentic, are underpinned by the unconscious, intertwined processes of splitting and blaming. Women sometimes split off undesirable aspects of the workplace, which repudiates gender inequality, or blame other women, which individualizes failure and responsibility for change. We explain that splitting and blaming enable some executive women to manage the anxiety evoked from threats to the neoliberal ideal of the workplace. This article thereby makes a contribution to existing postfeminist scholarship by integrating psychosocial approaches to the study of the psychic life of neoliberal executive women, by exploring why they appear unable to engage directly with and redress instances of gender discrimination in the workplace