Predicting arene rate coefficients with respect to hydroxyl and other free radicals in the gas-phase: a simple and effective method using a single topological descriptor

International audienceThe reactivity of aromatic compounds is of great relevance to pure and applied chemical disciplines, yet existing methods for estimating gas-phase rate coefficients for their reactions with free radicals lack accuracy and universality. Here a novel approach is taken, whereby strong relationships between rate coefficients of aromatic hydrocarbons and a Randi?-type topological index are investigated, optimized and developed into a method which requires no specialist software or computing power. Measured gas-phase rate coefficients for the reaction of aromatic hydrocarbons with OH radicals were correlated with a calculated Randi?-type index, and optimized by including a term for side chain length. Although this method is exclusively for use with hydrocarbons, it is more diverse than any single existing methodology since it incorporates alkenylbenzenes into correlations, and can be extended towards other radical species such as O(3P) (and tentatively NO3, H and Cl). A comparison (with species common to both techniques) is made between the topological approach advocated here and a popular approach based on electrophilic subsituent constants, where it compares favourably. A modelling study was carried out to assess the impact of using estimated rate coefficients as opposed to measured data in an atmospheric model. The difference in model output was negligible for a range of NOx concentrations, which implies that this method has utility in complex chemical models. Strong relationships (e.g. for OH, R2=0.96) between seemingly diverse compounds including benzene, multisubstituted benzenes with saturated, unsaturated, aliphatic and cyclic substitutions and the nonbenzenoid aromatic, azulene suggests that the Randi?-type index presented here represents a new and effective way of describing aromatic reactivity, based on a quantitative structure-activity relationship (QSAR)

The triple-peaked afterglow of GRB 210731A from X-ray to radio frequencies

GRB 210731A was a long-duration gamma-ray burst discovered by the Burst Alert Telescope (BAT) aboard the Neil Gehrels Swift observatory. Swift triggered the wide-field, robotic MeerLICHT optical telescope in Sutherland; it began observing the BAT error circle 286 seconds after the Swift trigger and discovered the optical afterglow of GRB 210731A in its first 60-second q-band exposure. Multi-colour observations of the afterglow with MeerLICHT revealed a light curve that showed three peaks of similar brightness within the first four hours. We present the results of our follow-up campaign and interpret our observations in the framework of the synchrotron forward shock model. We performed temporal and spectral fits to determine the spectral regime and external medium density profile, and performed detailed multi-wavelength theoretical modelling of the afterglow following the last optical peak at 0.2 days to determine the intrinsic blast wave parameters. We find a preference for a stellar wind density profile consistent with a massive star origin, while our theoretical modelling results in fairly typical shock microphysics parameters. Based on the energy released in gamma-rays and the kinetic energy in the blast wave, we determine a low radiative efficiency of ~0.02. The first peak in the optical light curve is likely the onset of the afterglow. We find that energy injection into the forward shock offers the simplest explanation for the subsequent light curve evolution, and that the blast wave kinetic energy increasing by a factor of ~1000 from the first peak to the last peak is indicative of substantial energy injection. Our highest-likelihood theoretical model overpredicts the 1.4 GHz flux by a factor of approximately three with respect to our upper limits, possibly implying a population of thermal electrons within the shocked region.Comment: 20 pages, 8 figures, accepted for publication in Astronomy & Astrophysic

African Dreams: Locating Urban Infrastructure in the 2030 Sustainable Developmental Agenda

This paper examines African urban infrastructure and service delivery as an entry point for connecting African aspirations with the harsh developmental imperatives of urban management, creating a dialogue between scholarly knowledge and sustainable development policy aspirations. We note a shift to multi-nodal urban governance and highlight the significance of the synthesis of social, economic and ecological values in a normative vision of what an African metropolis might aspire to by 2030. The sustainable development vision provides a useful stimulus for Africa’s urban poly-crisis, demanding fresh interdisciplinary and normatively explicit thinking, grounded in a practical and realistic understanding of Africa’s infrastructure and governance challenges

GW190814 follow-up with the optical telescope MeerLICHT

The Advanced LIGO and Virgo gravitational wave observatories detected a signal on 2019 August 14 during their third observing run, named GW190814. A large number of electromagnetic facilities conducted follow-up campaigns in the search for a possible counterpart to the gravitational wave event, which was made especially promising given the early source classification of a neutron star-black hole merger.We present the results of the GW follow-up campaign taken with the wide-field optical telescope MeerLICHT, located at the South African Astronomical Observatory Sutherland site. We use our results to constrain possible kilonova models. MeerLICHT observed more than 95% of the probability localisation each night for over a week in three optical bands (u,q,i) with our initial observations beginning almost 2 hours after the GW detection. We describe the search for new transients in MeerLICHT data and investigate how our limiting magnitudes can be used to constrain an AT2017gfo-like kilonova. A single new transient was found in our analysis of MeerLICHT data, which we exclude from being the electromagnetic counterpart to GW190814 due to the existence of a spatially unresolved source at the transient's coordinates in archival data. Using our limiting magnitudes, the confidence with which we can exclude the presence of an AT2017gfo-like kilonova at the distance of GW190814 was low ($<10^{-4}$).Comment: 19 pages, 6 figures, accepted by A&

Below the Belt? Territory and Development in China’s International Rise

China’s internationalization has been heralded by some as a new era of South–South cooperation. Yet such framings of development are pitched at an abstract space of the ‘global South’ which conceals more than it reveals. With some theory moving towards ontologies of ‘global development’, we need to capture both the connectedness and the local specificity of increasingly diffuse processes. This article sets out a more fine-grained understanding of how political territories and processes are imagined and produced by and through China’s internationalization, focusing on infrastructure as a ‘technology’ of territorialization. Much of the focus on China’s internationalization has been on state-to-state relations, but this obscures the ‘omni-channel politics’ that China practises. Using a critical literature review and illustrative case study, this article develops the idea of omni-channel politics to posit a view of ‘twisted’ territories in which political processes and development outcomes are more complex and contingent

Clarifying Values: An updated review

Background: Consensus guidelines have recommended that decision aids include a process for helping patients clarify their values. We sought to examine the theoretical and empirical evidence related to the use of values clarification methods in patient decision aids. Methods: Building on the International Patient Decision Aid Standards (IPDAS) Collaboration's 2005 review of values clarification methods in decision aids, we convened a multi-disciplinary expert group to examine key definitions, decision-making process theories, and empirical evidence about the effects of values clarification methods in decision aids. To summarize the current state of theory and evidence about the role of values clarification methods in decision aids, we undertook a process of evidence review and summary. Results: Values clarification methods (VCMs) are best defined as methods to help patients think about the desirability of options or attributes of options within a specific decision context, in order to identify which option he/she prefers. Several decision making process theories were identified that can inform the design of values clarification methods, but no single "best" practice for how such methods should be constructed was determined. Our evidence review found that existing VCMs were used for a variety of different decisions, rarely referenced underlying theory for their design, but generally were well described in regard to their development process. Listing the pros and cons of a decision was the most common method used. The 13 trials that compared decision support with or without VCMs reached mixed results: some found that VCMs improved some decision-making processes, while others found no effect. Conclusions: Values clarification methods may improve decision-making processes and potentially more distal outcomes. However, the small number of evaluations of VCMs and, where evaluations exist, the heterogeneity in outcome measures makes it difficult to determine their overall effectiveness or the specific characteristics that increase effectiveness

Design decisions for a real time, alcohol craving study using physio- and psychological measures

The current study was a pilot for an alcohol craving monitoring study with a biosensor (E4 wristband) and ecological momentary assessment (EMA) smartphone app. The E4 wristband was evaluated on compliance rates, usability, comfort and stigmatization. Two EMA methodologies (signal- and interval-contingent design) were compared on data variability, compliance and perceived burden. Results show that both EMA methodologies captured variability of craving and compliance rates were between medium to low. The perceived burden of the designs was high, in particular for the signal-contingent design. Participants wore the wristband ranging from occasionally to often and the usability was rated good. Many participants reported frequent questioning about the bracelet, which they indicated as positive. However, addicted individuals are expected not to appreciate this attention, we therefore propose to provide them with coping strategies. Efforts should be made to increase compliance, we therefore propose the interval contingent design with micro incentives

Ethylene supports colonization of plant roots by the mutualistic fungus Piriformospora indica

The mutualistic basidiomycete Piriformospora indica colonizes roots of mono- and dicotyledonous plants, and thereby improves plant health and yield. Given the capability of P. indica to colonize a broad range of hosts, it must be anticipated that the fungus has evolved efficient strategies to overcome plant immunity and to establish a proper environment for nutrient acquisition and reproduction. Global gene expression studies in barley identified various ethylene synthesis and signaling components that were differentially regulated in P. indica-colonized roots. Based on these findings we examined the impact of ethylene in the symbiotic association. The data presented here suggest that P. indica induces ethylene synthesis in barley and Arabidopsis roots during colonization. Moreover, impaired ethylene signaling resulted in reduced root colonization, Arabidopsis mutants exhibiting constitutive ethylene signaling, -synthesis or ethylene-related defense were hyper-susceptible to P. indica. Our data suggest that ethylene signaling is required for symbiotic root colonization by P. indica

Global inequality, human rights and power: a critique of Ulrich Beck's cosmopolitanism

This article is a critique of Ulrich Beck's advocacy of a cosmopolitan approach to global inequality and human rights. It is argued that cosmopolitanism does not bring a new and unique perspective on global inequality. In fact Beck's proposals on migration would reinforce inequality and anti-cosmopolitanism. It is argued that his `both/and' perspective on hybridization and contextual universalism is undermined by inequality, conflict and power that are glossed over in Beck's approach. I argue that human rights interventionism as advocated by Beck falls short of cosmopolitanism, in ways which are shown by qualifications about power and inequality that Beck himself makes in his arguments