Potential-Modulated Ion Distributions in the Back-to-Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer

Biphasic interfacial electron transfer (IET) reactions at polarisable liquid|liquid (L|L) interfaces underpin new approaches to electrosynthesis, redox electrocatalysis, bioelectrochemistry and artificial photosynthesis. Herein, using cyclic and alternating current voltammetry, we demonstrate that under certain experimental conditions, the biphasic 2-electron O2 reduction reaction can proceed by single-step IET between a reductant in the organic phase, decamethylferrocene, and interfacial protons in the presence of O2. Using this biphasic system, we demonstrate that the applied interfacial Galvani potential difference ΔwoØ provides no direct driving force to realise a thermodynamically uphill biphasic IET reaction in the mixed solvent region. We show that the onset potential for a biphasic single-step IET reaction does not correlate with the thermodynamically predicted standard Galvani IET potential and is instead closely correlated with the potential of zero charge at a polarised L|L interface. We outline that the applied ΔwoØ required to modulate the interfacial ion distributions, and thus kinetics of IET, must be optimised to ensure that the aqueous and organic redox species are present in substantial concentrations at the L|L interface simultaneously in order to react.M.D.S. acknowledges funding from Science Foundation Ireland (SFI) under grant no. 13/SIRG/2137 and the European Research Council through a Starting Grant (agreement no. 716792). A.G.-Q. acknowledges funding received from an Irish Research Council (IRC) Government of Ireland Postdoctoral Fellowship Award (grant number GOIPD/2018/252) and a Marie Skłodowska-Curie Postdoctoral Fellowship (Grant Number MSCA-IF-EF-ST 2020/101018277)

Fluorescent IGF-II analogues for FRET-based investigations into the binding of IGF-II to the IGF-1R

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.The interaction of IGF-II with the insulin receptor (IR) and type 1 insulin-like growth factor receptor (IGF-1R) has recently been identified as potential therapeutic target for the treatment of cancer. Understanding the interactions of IGF-II with these receptors is required for the development of potential anticancer therapeutics. This work describes an efficient convergent synthesis of native IGF-II and two nonnative IGF-II analogues with coumarin fluorescent probes incorporated at residues 19 and 28. These fluorescent analogues bind with nanomolar affinities to the IGF-1R and are suitable for use in fluorescence resonance energy transfer (FRET) studies. From these studies the F19Cou IGF-II and F28Cou IGF-II proteins were identified as good probes for investigating the binding interactions of IGF-II with the IGF-1R and its other high affinity binding partners

A justification of whistleblowing

Penultimate version accepted for publicationWhistleblowing is the act of disclosing information from a public or private organization in order to reveal cases of corruption that are of immediate or potential danger to the public. Blowing the whistle involves personal risk, especially when legal protection is absent, and charges of betrayal, which often come in the form of legal prosecution under treason laws. In this article we argue that whistleblowing is justified when disclosures are made with the proper intent and fulfill specific communicative constraints in addressing issues of public interest. Three communicative constraints of informativeness, truthfulness and evidence are discussed in this regard. We develop a ‘harm test’ to assess the intent for disclosures, concluding that it is not sufficient for justification. Along with the proper intent, a successful act of whistleblowing should provide information that serves the public interest. Taking cognizance of the varied conceptions of public interest, we present an account of public interest that fits the framework of whistleblowing disclosures. In particular, we argue that whistleblowing is justified inter alia when the information it conveys is of a presumptive interest for a public insofar as it reveals an instance of injustice or violation of a civil or political right done against and unbeknown to some members of a polity.Project: ‘Change of Direction. Fostering Whistleblowing in the Fight against Corruption’ co-funded by the Internal Security Fund of the European Union (Grant Agreement Number: HOME/2014/ISFP/AG/EFCE/7233); SFRH/BPD/108669/2015info:eu-repo/semantics/publishedVersio

Beta-blocker Therapy and Clinical Outcomes in Patients with Moderate COPD and Heightened Cardiovascular Risk:An Observational Sub-study of SUMMIT

Rationale: Cardiovascular disease is a common comorbidity in patients with chronic obstructive pulmonary disease (COPD). Although beta-blockers can be used safely in COPD, concerns remain regarding safety and efficacy interactions in patients using concomitant inhaled long-acting beta-agonists. Objectives: To compare the differential effects of long-acting beta agonist or inhaled corticosteroid use on clinical outcomes in patients with heightened cardiovascular risk treated and not treated with beta-blockers. Methods: We examined data from 16,485 participants in the Study to Understand Mortality and MorbidITy in COPD (SUMMIT) who were randomized to once daily inhaled fluticasone furoate (FF), vilanterol (VI), their combination (FF/VI), or placebo and examined the associations between treatment allocation and lung function, COPD exacerbations, cardiovascular events, and all-cause mortality stratified by baseline beta-blocker therapy. Results: Baseline beta-blocker therapy was used by 31% (n=5,159) of SUMMIT participants. There was no evidence of an interaction between baseline beta-blocker therapy and the association between inhaled treatments and FEV1 at 3 months (p=0.27), 6 months (p=0.14), or 12 months (p=0.33). The placebo-adjusted mean difference in post-bronchodilator FEV1 at 3 months in the VI alone group was 58 mL [95% confidence interval (CI) 38, 78] in those taking baseline beta-blocker therapy, and 51 mL [95%CI 38, 65], in those not taking baseline beta-blocker therapy. The placebo-adjusted mean difference in post-bronchodilator FEV1 at 3 months in the FF/VI group was 85 mL [95%CI 65, 105] in those taking baseline beta-blocker therapy, and 68 mL [95%CI 54, 82] in those not taking baseline beta-blocker therapy. Overall, there was no evidence of interactions by randomized treatment, including VI alone or in combination with FF, for COPD exacerbations (p=0.18), cardiovascular composite events (p=0.33), and all-cause mortality (p=0.41). Conclusions: There is no evidence to suggest that baseline beta-blocker therapy reduces the respiratory benefits or increases the cardiovascular risk of inhaled long-acting beta-agonists in patients with COPD and heightened cardiovascular risk. Clinical trial registered with ClinicalTrials.gov (NCT01313676

Crop Updates 2011 - Nutrition, Precision Agriculture & Climate and Forecasting

This session covers sixteen papers from different authors: Nutrition 1. Balance® used in conventional cropping practice with half of the upfront fertiliser rate can sustain crop yield and build soil biological fertility, Deb Archdeacon1, Andrew Gulliver2 and David Cullen2, 1Agronomica, Wellington Mill, WA, 2Custom Composts, Nambeelup, WA 2. Effects of potassium (K) supply on plant growth, potassium uptake and grain Yield in wheat grown in grey sand, Qifu Ma1, Richard Bell1, Ross Brennan2 and Craig Scanlan2, 1School of Environmental Science, Murdoch University, 2Department of Agriculture and Food 3. Improving fertiliser management: redefining the relationship between soil tests and crop responses for wheat in WA, Wen Chen1, 2, Ross Brennan2, Geoff Anderson2, Richard Bell1 and Mike Bolland2, 1School of Environmental Science, Murdoch University, 2Department of Agriculture and Food 4. Improved phosphorus and potassium management: redefining the soil test and lupin response relationships in WA, Wen Chen1, 2, Ross Brennan2, Geoff Anderson2, Richard Bell1 and Mike Bolland2, 1School of Environmental Science, Murdoch University, Western Australia, 2Department of Agriculture and Food 5. Converting phosphorus retention index (PRI) to phosphorus buffering index (PBI) for Western Australian soils, Peter Rees and Sandy Alexander, Summit Fertilizers 6. Variability of radiometric potassium and Colwell potassium relationships across the Great Southern, Frank D’Emden, Precision Agronomics Australia 7. Rotary spading and mouldboard ploughing of water-repellent sandplain soils fulfils promise, Stephen Davies, Craig Scanlan and Breanne Best, Department of Agriculture and Food 8. Soil nitrous oxide (N2O) fluxes are low from a grain legume crop grown in a semi-arid climate Louise Barton1, Klaus Butterbach-Bahl2, Ralph Kiese2 and Daniel Murphy1, 1 School of Earth & Environment, University of Western Australia, 2 Karlsruhe Institute of Technology, Institute for Meteorology & Climate Research, Garmisch-Partenkirchen, Germany, 9. Mouldboard ploughing of sandplain soils – more grain, fewer weeds, Peter Newman Department of Agriculture and Food Precision Agriculture 10.What’s preventing growers from implementing precision agriculture (PA)? Roger Mandel1, Roger Lawes2 and Michael Robertson2, 1Curtin University, 2CSIRO 11. On how many paddocks does precision agriculture (PA) deliver a return? Roger Lawes1, Michael Robertson1 and Roger Mandel2, 1CSIRO Ecosystem Sciences, Floreat, WA, 2Curtin University 12. Demonstration pf precision agriculture (PA) principles in the Great Southern, Western Australia, Derk Bakker1, Jeremy Lemon1, Alison Lacey1, John Paul Collins1, Roger Mandel2, Frank D’Emden3, Glen Riethmuller1, 1Department of Agriculture and Food, 2Curtin University, 3Precision Agronomics Australia Climate and Forecasting 13. Statistical seasonal rainfall forecasts for south west Australia, Fiona H Evans Department of Agriculture of Food 14. How has changing climate recently affected Western Australia’s capacity to increase crop productivity and water use efficiency? David Stephens, Department of Agriculture and Food 15. Is Yield Prophet® a useful tool in Western Australia? — an agribusiness perspective, Caroline Peek, Department of Agriculture and Food 16. A season of Yield Prophet® — how it saw the dry, Tim Scanlon and Caroline Peek Department of Agriculture of Foo

Widespread extrahippocampal NAA/(Cr+Cho) abnormalities in TLE with and without mesial temporal sclerosis

MR spectroscopy has demonstrated extrahippocampal NAA/(Cr+Cho) reductions in medial temporal lobe epilepsy with (TLE-MTS) and without (TLE-no) mesial temporal sclerosis. Because of the limited brain coverage of those previous studies, it was, however, not possible to assess differences in the distribution and extent of these abnormalities between TLE-MTS and TLE-no. This study used a 3D whole brain echoplanar spectroscopic imaging (EPSI) sequence to address the following questions: (1) Do TLE-MTS and TLE-no differ regarding severity and distribution of extrahippocampal NAA/(Cr+Cho) reductions? (2) Do extrahippocampal NAA/(Cr+Cho) reductions provide additional information for focus lateralization? Forty-three subjects (12 TLE-MTS, 13 TLE-no, 18 controls) were studied with 3D EPSI. Statistical parametric mapping (SPM2) was used to identify regions of significantly decreased NAA/(Cr+Cho) in TLE groups and in individual patients. TLE-MTS and TLE-no had widespread extrahippocampal NAA/(Cr+Cho) reductions. NAA/(Cr+Cho) reductions had a bilateral fronto-temporal distribution in TLE-MTS and a more diffuse, less well defined distribution in TLE-no. Extrahippocampal NAA/(Cr+Cho) decreases in the single subject analysis showed a large inter-individual variability and did not provide additional focus lateralizing information. Extrahippocampal NAA/(Cr+Cho) reductions in TLE-MTS and TLE-no are neither focal nor homogeneous. This reduces their value for focus lateralization and suggests a heterogeneous etiology of extrahippocampal spectroscopic metabolic abnormalities in TLE

A hard x-ray photoemission study of transparent conducting fluorine-doped tin dioxide

Fluorine-doped tin oxide (FTO) is a commercially successful transparent conducting oxide with very good electrical (resistivities < 1×103 Ω·cm) and optical properties (transmittance > 85%). These properties coupled with cheap and large-scale deposition on float-glass lines means FTO has found commercial use in, for example, low emissivity windows and solar cells. However, despite its widespread application, a detailed understanding is lacking of the doping and defects in FTO. Recent work [1] has suggested that the fluorine interstitial plays a major role in limiting the conductivity of FTO. Here we present synchrotron radiation high energy x-ray photoemission spectroscopy (XPS) of the fluorine 1s core level of FTO films without in situ surface preparation. This probes deeper than standard XPS and shows that the fluorine interstitial is present not just at the surface of the films and is not an artefact of argon ion sputtering for surface preparation

Roadmap on Photovoltaic Absorber Materials for Sustainable Energy Conversion

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfil ambitions for net-zero carbon dioxide equivalent (CO2eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the photovoltaics community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.Comment: 160 pages, 21 figure