NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors.

Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors.A.C.F., J.M.G., C.M., P.M.B., H.W., and C.P.G. acknowledge the Sims Scholarship (A.C.F), EPSRC (via the Supergen consortium, J.M.G.), The School of Physical Sciences (University of Cambridge) for funding through an Oppen- heimer Research Fellowship (C.M.), The Marie Curie FP7 International Incoming Fellowship (P.M.B.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. P.S. acknowledges support from the European Research Council (ERC, Advanced Grant, ERC-2011-AdG, Project 291543−IONACES).This is the final version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jacs.5b03958

Cycling Li-O₂ batteries via LiOH formation and decomposition.

The rechargeable aprotic lithium-air (Li-O2) battery is a promising potential technology for next-generation energy storage, but its practical realization still faces many challenges. In contrast to the standard Li-O2 cells, which cycle via the formation of Li2O2, we used a reduced graphene oxide electrode, the additive LiI, and the solvent dimethoxyethane to reversibly form and remove crystalline LiOH with particle sizes larger than 15 micrometers during discharge and charge. This leads to high specific capacities, excellent energy efficiency (93.2%) with a voltage gap of only 0.2 volt, and impressive rechargeability. The cells tolerate high concentrations of water, water being the dominant proton source for the LiOH; together with LiI, it has a decisive impact on the chemical nature of the discharge product and on battery performance.This work was partially supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Batteries for Advanced Transportation Technologies (BATT) Program subcontract #7057154 (WY, ML, PB), EPSRC (TL), Johnson Matthey (AM) and Marie Curie Actions (PB and ML).This is the author accepted manuscript. The final version is available from AAAS via http://dx.doi.org/10.1126/science.aac773

Measuring and Correcting Wind-Induced Pointing Errors of the Green Bank Telescope Using an Optical Quadrant Detector

Wind-induced pointing errors are a serious concern for large-aperture high-frequency radio telescopes. In this paper, we describe the implementation of an optical quadrant detector instrument that can detect and provide a correction signal for wind-induced pointing errors on the 100m diameter Green Bank Telescope (GBT). The instrument was calibrated using a combination of astronomical measurements and metrology. We find that the main wind-induced pointing errors on time scales of minutes are caused by the feedarm being blown along the direction of the wind vector. We also find that wind-induced structural excitation is virtually non-existent. We have implemented offline software to apply pointing corrections to the data from imaging instruments such as the MUSTANG 3.3 mm bolometer array, which can recover ~70% of sensitivity lost due to wind-induced pointing errors. We have also performed preliminary tests that show great promise for correcting these pointing errors in real-time using the telescope's subreflector servo system in combination with the quadrant detector signal.Comment: 17 pages, 11 figures; accepted for publication in PAS

High-Q Si3N4 Ring Resonators for Locking 780nm GaAs-Based Distributed Feedback Laser

High-Q microring resonators have applications in gyroscopes, frequency comb generation, and feedback systems to control narrow linewidth integrated lasers [1–3]. This paper demonstrates the highest Q values measured for microring resonators at 780 nm wavelength. These sub mm integrated cavities can be used to provide an error signal for locking a distributed feedback laser (DFB), Fig. 1(a), using the Pound-Drever-Hall (PDH) method. High stability DFBs can also be achieved using a micro-electro-mechanical system (MEMS) cell containing 87 Rb vapour and taking advantage of the absorption line at 780.24 nm. This provides an absolute reference for locking the laser but only to the 87 Rb transition wavelengths. The microring resonator can be tailor made for any wavelength but is susceptible to thermal effects; this could in part be overcome using a top cladding with a thermo-optic coefficient that counteracts that of the waveguide core

Human Activity Mediates a Trophic Cascade Caused by Wolves

Experimental evidence of trophic cascades initiated by large vertebrate predators is rare in terrestrial ecosystems. A serendipitous natural experiment provided an opportunity to test the trophic cascade hypothesis for wolves (Canis lupus) in Banff National Park, Canada. The first wolf pack recolonized the Bow Valley of Banff National Park in 1986. High human activity partially excluded wolves from one area of the Bow Valley (low-wolf area), whereas wolves made full use of an adjacent area (high-wolf area). We investigated the effects of differential wolf predation between these two areas on elk (Cervus elaphus) population density, adult female survival, and calf recruitment; aspen (Populus tremuloides) recruitment and browse intensity; willow (Salix spp.) production, browsing intensity, and net growth; beaver (Castor canadensis) density; and riparian songbird diversity, evenness, and abundance. We compared effects of recolonizing wolves on these response variables using the log response ratio between the low-wolf and high-wolf treatments. Elk population density diverged over time in the two treatments, such that elk were an order of magnitude more numerous in the low-wolf area compared to the high-wolf area at the end of the study. Annual survival of adult female elk was 62% in the high-wolf area vs. 89% in the low-wolf area. Annual recruitment of calves was 15% in the high-wolf area vs. 27% without wolves. Wolf exclusion decreased aspen recruitment, willow production, and increased willow and aspen browsing intensity. Beaver lodge density was negatively correlated to elk density, and elk herbivory had an indirect negative effect on riparian songbird diversity and abundance. These alternating patterns across trophic levels support the wolf-caused trophic cascade hypothesis. Human activity strongly mediated these cascade effects, through a depressing effect on habitat use by wolves. Thus, conservation strategies based on the trophic importance of large carnivores have increased support in terrestrial ecosystems. Read More: http://www.esajournals.org/doi/full/10.1890/04-126

In situ, real-time visualization of electrochemistry using magnetic resonance imaging

The drive to develop better electrochemical energy storage devices requires the development of not only new materials, but also better understanding of the underpinning chemical and dynamical processes within such devices during operation, for which new analytical techniques are required. Currently, there are few techniques that can probe local composition and transport in the electrolyte during battery operation. In this paper, we report a novel application of magnetic resonance imaging (MRI) for probing electrochemical processes in a model electrochemical cell. Using MRI, the transport and zinc and oxygen electrochemistry in an alkaline electrolyte, typical of that found in zinc-air batteries, are investigated. Magnetic resonance relaxation maps of the electrolyte are used to visualize the chemical composition and electrochemical processes occurring during discharge in this model metal-air battery. Such experiments will be useful in the development of new energy storage/conversion devices, as well as other electrochemical technologies

Cytoplasmic p53 couples oncogene-driven glucose metabolism to apoptosis and is a therapeutic target in glioblastoma.

Cross-talk among oncogenic signaling and metabolic pathways may create opportunities for new therapeutic strategies in cancer. Here we show that although acute inhibition of EGFR-driven glucose metabolism induces only minimal cell death, it lowers the apoptotic threshold in a subset of patient-derived glioblastoma (GBM) cells. Mechanistic studies revealed that after attenuated glucose consumption, Bcl-xL blocks cytoplasmic p53 from triggering intrinsic apoptosis. Consequently, targeting of EGFR-driven glucose metabolism in combination with pharmacological stabilization of p53 with the brain-penetrant small molecule idasanutlin resulted in synthetic lethality in orthotopic glioblastoma xenograft models. Notably, neither the degree of EGFR-signaling inhibition nor genetic analysis of EGFR was sufficient to predict sensitivity to this therapeutic combination. However, detection of rapid inhibitory effects on [18F]fluorodeoxyglucose uptake, assessed through noninvasive positron emission tomography, was an effective predictive biomarker of response in vivo. Together, these studies identify a crucial link among oncogene signaling, glucose metabolism, and cytoplasmic p53, which may potentially be exploited for combination therapy in GBM and possibly other malignancies

Towards incorporation of blue carbon in Falkland Islands marine spatial planning: a multi-tiered approach

Ecosystem-based conservation that includes carbon sinks, alongside a linked carbon credit system, as part of a nature-based solution to combating climate change, could help reduce greenhouse gas levels and therefore the impact of their emissions. Blue carbon habitats and pathways can also facilitate biodiversity retention, aiding sustainable fisheries and island economies. However, robust blue carbon research is often limited at the scale of regional governance and management, lacking both incentives and facilitation of policy-integration. The remote and highly biodiverse coastal ecosystems and surrounding continental shelf can be used to better inform long-term ecosystem-based management in the vast South Atlantic Ocean and sub-Antarctic, to synergistically protect both unique biodiversity and inform on the magnitude of nature-based benefits they provide. Understanding key ecosystem information such as their location, extent, and condition of habitat types, will be critical in understanding carbon pathways to sequestration, threats to this, and vulnerability. This paper considers the current status of blue carbon data and information available, and what is still required before blue carbon can be used as a conservation management tool integrated in national Marine Spatial Planning (MSP) initiatives. Our research indicates that the data and information gathered has enabled baselines for a number of different blue carbon ecosystems, and indicated potential threats and vulnerability that need to be managed. However, significant knowledge gaps remain across habitats, such as salt marsh, mudflats and the mesophotic zones, which hinders meaningful progress on the ground where it is needed most