Stimulus-Mediated Ultrastable Radical Formation

Organic radicals are reactive, often short-lived species typically formed through either the addition of a chemical agent or photochemical means. On account of their open-shell electronic structure they have attracted attention based upon their magnetic properties and desirable spectroscopic behaviour. Redox sensitive molecules such as viologen (V) undergo one-electron reductions to form radical species. These species hold significant potential in myriad applications but are limited as they are rapidly quenched by oxygen in air. Using methyl viologen as an example, we show that the MV radical (MV+·) can be formed through electrochemical, chemical, photochemical and a novel thermal stimulus in various Deep Eu- tectic Solvents (DES) and was found to be exceptionally stable. The conductive properties of DES allowed for fabrication of an aerobic electrochromic device through a straightforward, economical approach. Our report represents a unique approach to extend reactive radical lifetimes in air without alteration of the parent structure.J.A.M. would like to acknowledge the EPSRC for a PhD studentship (EP/K503009/1). O.A.S. acknowledges ERC Consolidator grant CAM-RIG (No.726470) and UK Engineering and Physical Sciences Research Council grant EP/L027151/1. M.F.K. and E.R. acknowledge Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group and the EPSRC (IAA Follow-on Fund)

Studying the accretion geometry of EXO 2030+375 at luminosities close to the propeller regime

The Be X-ray binary EXO 2030+375 was in an extended low luminosity state during most of 2016. We observed this state with NuSTAR and Swift, supported by INTEGRAL observations as well as optical spectroscopy with the NOT. We present a comprehensive spectral and timing analysis of these data here to study the accretion geometry and investigate a possible onset of the propeller effect. The H-alpha data show that the circumstellar disk of the Be-star is still present. We measure equivalent widths similar to values found during more active phases in the past, indicating that the low-luminosity state is not simply triggered by a smaller Be disk. The NuSTAR data, taken at a 3-78 keV luminosity of ~6.8e35 erg/s (for a distance of 7.1 kpc), are well described by standard accreting pulsar models, such as an absorbed power-law with a high-energy cutoff. We find that pulsations are still clearly visible at these luminosities, indicating that accretion is continuing despite the very low mass transfer rate. In phase-resolved spectroscopy we find a peculiar variation of the photon index from ~1.5 to ~2.5 over only about 3% of the rotational period. This variation is similar to that observed with XMM-Newton at much higher luminosities. It may be connected to the accretion column passing through our line of sight. With Swift/XRT we observe luminosities as low as 1e34 erg/s during which the data quality did not allow us to search for pulsations, but the spectrum is much softer and well described by either a blackbody or soft power-law continuum. This softer spectrum might be due to the fact that accretion has been stopped by the propeller effect and we only observe the neutron star surface cooling.Comment: 11 pages, 6 figures, accepted for publication in A&A (v2 including language edits

Staring at 4U 1909+07 with Suzaku (Research Note)

We present an analysis of the neutron star High Mass X-ray Binary (HMXB) 4U 1909+07 mainly based on Suzaku data. We extend the pulse period evolution, which behaves in a random-walk like manner, indicative of direct wind accretion. Studying the spectral properties of 4U 1909+07 between 0.5 to 90keV we find that a power-law with an exponential cutoff can describe the data well, when additionally allowing for a blackbody or a partially covering absorber at low energies. We find no evidence for a cyclotron resonant scattering feature (CRSF), a feature seen in many other neutron star HMXBs sources. By performing pulse phase resolved spectroscopy we investigate the origin of the strong energy dependence of the pulse profile, which evolves from a broad two-peak profile at low energies to a profile with a single, narrow peak at energies above 20keV. Our data show that it is very likely that a higher folding energy in the high energy peak is responsible for this behavior. This in turn leads to the assumption that we observe the two magnetic poles and their respective accretion columns at different phases, and that these accretions column have slightly different physical conditions

Selective photocatalytic CO2_2 reduction in water through anchoring of a molecular Ni catalyst on CdS nanocrystals

Photocatalytic conversion of CO$_2$ into carbonaceous feedstock chemicals is a promising strategy to mitigate greenhouse gas emissions and simultaneously store solar energy in chemical form. Photocatalysts for this transformation are typically based on precious metals and operate in nonaqueous solvents to suppress competing H$_2$ generation. In this work, we demonstrate selective visible-light-driven CO$_2$ reduction in water using a synthetic photocatalyst system that is entirely free of precious metals. We present a series of self-assembled nickel terpyridine complexes as electrocatalysts for the reduction of CO$_2$ to CO in organic media. Immobilization on CdS quantum dots allows these catalysts to be active in purely aqueous solution and photocatalytically reduce CO$_2$ with >90% selectivity under UV-filtered simulated solar light irradiation (AM 1.5G, 100 mW cm$^{–2}$, λ > 400 nm, pH 6.7, 25 °C). Correlation between catalyst immobilization efficiency and product selectivity shows that anchoring the molecular catalyst on the semiconductor surface is key in controlling the selectivity for CO$_2$ reduction over H$_2$ evolution in aqueous solution.Christian Doppler Research Association, OMV group, Isaac Newton Trust, the German Research Foundation, the World Premier International Research Center Initiative, MEXT, Japa

ZnSe Nanorods as Visible-Light Absorbers for Photocatalytic and Photoelectrochemical H2 Evolution in Water.

A precious-metal- and Cd-free photocatalyst system for efficient H2 evolution from aqueous protons with a performance comparable to Cd-based quantum dots is presented. Rod-shaped ZnSe nanocrystals (nanorods, NRs) with a Ni(BF4 )2 co-catalyst suspended in aqueous ascorbic acid evolve H2 with an activity up to 54±2 mmol H 2  gZnSe -1  h-1 and a quantum yield of 50±4 % (λ=400 nm) under visible light illumination (AM 1.5G, 100 mW cm-2 , λ>400 nm). Under simulated full-spectrum solar irradiation (AM 1.5G, 100 mW cm-2 ), up to 149±22 mmol H 2  gZnSe -1  h-1 is generated. Significant photocorrosion was not noticeable within 40 h and activity was even observed without an added co-catalyst. The ZnSe NRs can also be used to construct an inexpensive delafossite CuCrO2 photocathode, which does not rely on a sacrificial electron donor. Immobilized ZnSe NRs on CuCrO2 generate photocurrents of around -10 μA cm-2 in an aqueous electrolyte solution (pH 5.5) with a photocurrent onset potential of approximately +0.75 V vs. RHE. This work establishes ZnSe as a state-of-the-art light absorber for photocatalytic and photoelectrochemical H2 generation.Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group, the EPSRC NanoDTC, EPSRC Underpinning Multi-User Equipment Grant (EP/P030467/1), the Erasmus+ program (D.W.), the Erasmus program (A.S.) and the World Premier International Research Center Initiative, MEXT, Japa

Solar-driven reforming of lignocellulose to H2_{2} with a CdS/CdOx_{x} photocatalyst

Lignocellulose is Earth’s most abundant form of biomass and its valorization to H$_{2}$ is a key objective for the generation of renewable fuels. Solar-driven photocatalytic reforming of lignocellulose to H$_{2}$ at ambient temperature offers a sustainable route towards this goal, but this reaction is currently limited to noble-metal-containing systems that operate with low activity under ultraviolet light. Here, we report the light-driven photoreforming of cellulose, hemicellulose and lignin to H$_{2}$ using semiconducting cadmium sulfide quantum dots in alkaline aqueous solution. We show that basic conditions cause these dots to become coated with oxide/hydroxide in situ, presenting a strategy to improve their photocatalytic performance. The system operates under visible light, is stable beyond six days and is even able to reform unprocessed lignocellulose, such as wood and paper, under solar irradiation at room temperature, presenting an inexpensive route to drive aqueous proton reduction to H$_{2}$ through waste biomass oxidation.This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group (to E.R.), the EPSRC (DTA studentships for D.W.W. and T.E.R), the Isaac Newton Trust, the German Research Foundation (to M.F.K.), the World Premier Institute Research Center Initiative (WPI), MEXT, Japan (to K.L.O.) and a Marie Curie Research fellowship (to K.H.L., GAN 701192 - VSHER)

Tuning Product Selectivity for Aqueous CO2 Reduction with a Mn(bipyridine)-pyrene Catalyst Immobilized on a Carbon Nanotube Electrode

The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different intermediates were identified as responsible for the change in selectivity of the heterogenized Mn catalyst. The formation of a dimeric Mn0 species at higher surface loading was shown to preferentially lead to CO formation, whereas at lower surface loading the electrochemical generation of a monomeric Mn-hydride is suggested to greatly enhance the production of formate. These results emphasize the advantages of integrating molecular catalysts onto electrode surfaces for enhancing catalytic activity while allowing excellent control and a deeper understanding of the catalytic mechanisms.This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group, the EPSRC (DTA studentship for T.E.R.), the European Union’s Horizon 2020 research and innovation program (Marie SklodowskaCurie IF for K.H.L., GAN 701192), and an ERC Consolidator Grant “MatEnSAP” (GAN 682833). I.Z. is indebted to the German Research Foundation (DFG) for financial support within the cluster of excellence EXC 314: Unifying concepts in catalysis, “UniCat”

A Plasmodium membrane receptor platform integrates cues for egress and invasion in blood forms and activation of transmission stages

Critical events in the life cycle of malaria-causing parasites depend on cyclic guanosine monophosphate homeostasis by guanylyl cyclases (GCs) and phosphodiesterases, including merozoite egress or invasion of erythrocytes and gametocyte activation. These processes rely on a single GCalpha, but in the absence of known signaling receptors, how this pathway integrates distinct triggers is unknown. We show that temperature-dependent epistatic interactions between phosphodiesterases counterbalance GCalpha basal activity preventing gametocyte activation before mosquito blood feed. GCalpha interacts with two multipass membrane cofactors in schizonts and gametocytes: UGO (unique GC organizer) and SLF (signaling linking factor). While SLF regulates GCalpha basal activity, UGO is essential for GCalpha up-regulation in response to natural signals inducing merozoite egress and gametocyte activation. This work identifies a GC membrane receptor platform that senses signals triggering processes specific to an intracellular parasitic lifestyle, including host cell egress and invasion to ensure intraerythrocytic amplification and transmission to mosquitoes