Solar Energy Storage by Molecular Norbornadiene–Quadricyclane Photoswitches:Polymer Film Devices

Devices that can capture and convert sunlight into stored chemical energy are attractive candidates for future energy technologies. A general challenge is to combine efficient solar energy capture with high energy densities and energy storage time into a processable composite for device application. Here, norbornadiene (NBD)–quadricyclane (QC) molecular photoswitches are embedded into polymer matrices, with possible applications in energy storing coatings. The NBD–QC photoswitches that are capable of absorbing sunlight with estimated solar energy storage efficiencies of up to 3.8% combined with attractive energy storage densities of up to 0.48 MJ kg −1 . The combination of donor and acceptor units leads to an improved solar spectrum match with an onset of absorption of up to 529 nm and a lifetime (t 1/2 ) of up to 10 months. The NBD–QC systems with properties matched to a daily energy storage cycle are further investigated in the solid state by embedding the molecules into a series of polymer matrices revealing that polystyrene is the preferred choice of matrix. These polymer devices, which can absorb sunlight and over a daily cycle release the energy as heat, are investigated for their cyclability, showing multicycle reusability with limited degradation that might allow them to be applied as window laminates

Color Gradients and Surface Brightness Profiles of Galaxies in the Hubble Deep Field-North

We fit elliptical isophotes to the Hubble Deep Field-North WFPC-2 and NICMOS data to study the rest-frame UV_{218}-U_{300} color profiles and rest-frame B surface brightness profiles of 33 intermediate redshift galaxies (0.5 <= z <= 1.2) with I_{814} < 25 and 50 high redshift galaxies (2.0 <= z <= 3.5) with H_{160}< 27. From the weighted least-squares fit to the color profiles we find that, at intermediate redshifts, the galaxies possess negative color gradients indicating a reddening towards the center of the profile similar to local samples whereas, at high redshifts, the galaxies possess positive color gradients. This indicates that star formation is more centrally concentrated in the distant galaxy sample which differs from the prevalent mode of extended disk star formation that we observe in the local universe. Additionally, we find that it is critical to correct for PSF effects when evaluating the surface brightness profiles since at small scale lengths and faint magnitudes, an r^{1/4} profile can be smoothed out substantially to become consistent with an exponential profile. After correcting for PSF effects, we find that at higher look-back time, the fraction of galaxies possessing exponential profiles have slightly decreased while the fraction of galaxies possessing r^{1/4} profiles have slightly increased. Our results also suggest a statistically insignificant increase in the fraction of peculiar/irregular type galaxies. We compare our results with recent semi-analytical models which treat galaxy formation and evolution following the cold dark matter hierarchical framework.Comment: 31 pages, 10 JPEG figures. To be published in AJ Vol. 124, October 200

A Hückel source-sink-potential theory of Pauli spin blockade in molecular electronic devices

This paper shows how to include Pauli (exclusion principle) effects within a treatment of ballistic molecular conduction that uses the tight-binding Hückel Hamiltonian and the source-sink-potential (SSP) method. We take into account the many-electron ground-state of the molecule and show that we can discuss ballistic conduction for a specific molecular device in terms of four structural polynomials. In the standard one-electron picture, these are characteristic polynomials of vertex-deleted graphs, with spectral representations in terms of molecular-orbital eigenvectors and eigenvalues. In a more realistic many-electron picture, the spectral representation of each polynomial is retained but projected into the manifold of unoccupied spin-orbitals. Crucially, this projection preserves interlacing properties. With this simple reformulation, selection rules for device transmission, expressions for overall transmission, and partition of transmission into bond currents can all be mapped onto the formalism previously developed. Inclusion of Pauli spin blockade, in the absence of external perturbations, has a generic effect (suppression of transmission at energies below the Fermi level) and specific effects at anti-bonding energies, which can be understood using our previous classification of inert and active shells. The theory predicts the intriguing phenomenon of Pauli perfect reflection whereby, once a critical electron count is reached, some electronic states of devices can give total reflection of electrons at all energies

Dimethyl fumarate in patients admitted to hospital with COVID-19 (RECOVERY): a randomised, controlled, open-label, platform trial

Dimethyl fumarate (DMF) inhibits inflammasome-mediated inflammation and has been proposed as a treatment for patients hospitalised with COVID-19. This randomised, controlled, open-label platform trial (Randomised Evaluation of COVID-19 Therapy [RECOVERY]), is assessing multiple treatments in patients hospitalised for COVID-19 (NCT04381936, ISRCTN50189673). In this assessment of DMF performed at 27 UK hospitals, adults were randomly allocated (1:1) to either usual standard of care alone or usual standard of care plus DMF. The primary outcome was clinical status on day 5 measured on a seven-point ordinal scale. Secondary outcomes were time to sustained improvement in clinical status, time to discharge, day 5 peripheral blood oxygenation, day 5 C-reactive protein, and improvement in day 10 clinical status. Between 2 March 2021 and 18 November 2021, 713 patients were enroled in the DMF evaluation, of whom 356 were randomly allocated to receive usual care plus DMF, and 357 to usual care alone. 95% of patients received corticosteroids as part of routine care. There was no evidence of a beneficial effect of DMF on clinical status at day 5 (common odds ratio of unfavourable outcome 1.12; 95% CI 0.86-1.47; p = 0.40). There was no significant effect of DMF on any secondary outcome

Dimethyl fumarate in patients admitted to hospital with COVID-19 (RECOVERY): a randomised, controlled, open-label, platform trial

Dimethyl fumarate (DMF) inhibits inflammasome-mediated inflammation and has been proposed as a treatment for patients hospitalised with COVID-19. This randomised, controlled, open-label platform trial (Randomised Evaluation of COVID-19 Therapy [RECOVERY]), is assessing multiple treatments in patients hospitalised for COVID-19 (NCT04381936, ISRCTN50189673). In this assessment of DMF performed at 27 UK hospitals, adults were randomly allocated (1:1) to either usual standard of care alone or usual standard of care plus DMF. The primary outcome was clinical status on day 5 measured on a seven-point ordinal scale. Secondary outcomes were time to sustained improvement in clinical status, time to discharge, day 5 peripheral blood oxygenation, day 5 C-reactive protein, and improvement in day 10 clinical status. Between 2 March 2021 and 18 November 2021, 713 patients were enroled in the DMF evaluation, of whom 356 were randomly allocated to receive usual care plus DMF, and 357 to usual care alone. 95% of patients received corticosteroids as part of routine care. There was no evidence of a beneficial effect of DMF on clinical status at day 5 (common odds ratio of unfavourable outcome 1.12; 95% CI 0.86-1.47; p = 0.40). There was no significant effect of DMF on any secondary outcome

From shame to blame: institutionalising oppression through the moralisation of mental distress in austerity England

This paper interrogates qualitative data regarding the changing experiences of men- tal health service and welfare state interventions for those who self-identify as experiencing long-term mental distress. We focus on austerity-related reforms in the English welfare and mental health policy architecture to explore the socio-cultural and material bases of benefit claims-making in relation to long-term illness and incapac- ity. Recent neoliberal social policy reforms contest the ontological status of mental distress, in effect recasting distress as a ‘moral’ status. This tendency is reinforced via three primary dynamics in contemporary mental health and welfare policy: the delegitimisation of sick role status in relation to mental distress; the foregrounding of individual responsibility and concomitant re-orientation of services towards self-help; and an increasing punitive conditionality. These intersecting processes represent an institutionalisation of ‘blame’ in various policy contexts (Scambler in Sociol Health Illn 31(3): 441–455, 2009; Sociol Rev Monogr 66(4):766–782, 2018), the moral stigmatisation of mental distress and escalating experiences of oppression for mental health service users and welfare recipients. Shifting conceptions of distress are thereby entwined with transformations in social policy regimes and political economies. Presenting distress as a personal failure legitimates austerity-related restrictions on benefit and service entitlements as part of a wider project of neoliberal welfare state transformation

CdS/ZnS core-shell nanocrystal photosensitizers for visible to UV upconversion

Herein we report the first example of nanocrystal (NC) sensitized triplet-triplet annihilation based photon upconversion from the visible to ultraviolet (vis-to-UV). Many photocatalyzed reactions, such as water splitting, require UV photons in order to function efficiently. Upconversion is one possible means of extending the usable range of photons into the visible. Vis-to-UV upconversion is achieved with CdS/ZnS core-shell NCs as the sensitizer and 2,5-diphenyloxazole (PPO) as annihilator and emitter. The ZnS shell was crucial in order to achieve any appreciable upconversion. From time resolved photoluminescence and transient absorption measurements we conclude that the ZnS shell affects the NC and triplet energy transfer (TET) from NC to PPO in two distinct ways. Upon ZnS growth the surface traps are passivated thus increasing the TET. The shell, however, also acts as a tunneling barrier for TET, reducing the efficiency. This leads to an optimal shell thickness where the upconversion quantum yield (Phi(UC)\u27) is maximized. Here the maximum Phi(UC)\u27 was determined to be 5.2 +/- 0.5% for 4 monolayers of ZnS shell on CdS NCs