Surface science of soft scorpionates

The chemisorption of the soft scorpionate Li[PhTmMe] onto silver and gold surfaces is reported. Surface enhanced Raman spectroscopy in combination with the Raman analysis of suitable structural models, namely, [Cu(κ3-S,S,S-PhTmMe)(PCy3)], [Ag(κ3-S,S,S-PhTmMe)(PCy3)], [Ag(κ2-S,S-PhTmMe)(PEt3)], and [Au(κ1-S-PhTmMe)(PCy3)], are employed to identify the manner in which this potentially tridentate ligand binds to these surfaces. On colloidal silver surface-enhanced Raman spectroscopy (SERS) spectra are consistent with PhTmMe binding in a didentate fashion to the surface, holding the aryl group in close proximity to the surface. In contrast, on gold colloid, we observe that the species prefers a monodentate coordination in which the aryl group is not in close proximity to the surface

The Internet and HIV study: design and methods

BACKGROUND: The Internet provides a new meeting ground, especially for gay men, that did not exist in the early 1990s. Several studies have found increased levels of high risk sexual behaviour and sexually transmissible infections (STI) among gay men who seek sex on the Internet, although the underlying processes are not fully understood. Research funded by the UK Medical Research Council (2002–2004) provided the opportunity to consider whether the Internet represents a new sexual risk environment for gay and bisexual men living in London. METHODS: The objectives of the Internet and HIV study are to: (i) measure the extent to which gay men living in London seek sexual partners on the Internet; (ii) compare the characteristics of London gay men who do and do not seek sex on the Internet; (iii) examine whether sex with Internet-partners is less safe than with other sexual partners; (iv) compare use of the Internet with other venues where men meet sexual partners; (v) establish whether gay men use the Internet to actively seek partners for unprotected anal intercourse; (vi) determine the potential for using the Internet for HIV prevention. These objectives have been explored using quantitative and qualitative research methods in four samples of London gay men recruited and interviewed both online and offline. The four samples were: (i) gay men recruited through Internet chat rooms and profiles; (ii) HIV positive gay men attending an NHS hospital outpatients clinic; (iii) gay men seeking an HIV test in an NHS HIV testing or sexual health clinic; (iv) gay men recruited in the community. RESULTS: Quantitative data were collected by means of confidential, anonymous self-administered questionnaires (n>4000) completed on-line by the Internet sample. Qualitative data were collected by means of one-to-one interviews (n = 128) conducted either face-to-face or on-line. CONCLUSION: The strength of the Internet and HIV study is its methodological plurality, drawing on both qualitative and quantitative research among online and offline samples, as well as taking advantage of recent advances in web survey design. The study's findings will help us better understand the role of the Internet in relation to gay men's sexual practic

Genome Analyses of an Aggressive and Invasive Lineage of the Irish Potato Famine Pathogen

Pest and pathogen losses jeopardise global food security and ever since the 19th century Irish famine, potato late blight has exemplified this threat. The causal oomycete pathogen, Phytophthora infestans, undergoes major population shifts in agricultural systems via the successive emergence and migration of asexual lineages. The phenotypic and genotypic bases of these selective sweeps are largely unknown but management strategies need to adapt to reflect the changing pathogen population. Here, we used molecular markers to document the emergence of a lineage, termed 13_A2, in the European P. infestans population, and its rapid displacement of other lineages to exceed 75% of the pathogen population across Great Britain in less than three years. We show that isolates of the 13_A2 lineage are among the most aggressive on cultivated potatoes, outcompete other aggressive lineages in the field, and overcome previously effective forms of plant host resistance. Genome analyses of a 13_A2 isolate revealed extensive genetic and expression polymorphisms particularly in effector genes. Copy number variations, gene gains and losses, amino-acid replacements and changes in expression patterns of disease effector genes within the 13_A2 isolate likely contribute to enhanced virulence and aggressiveness to drive this population displacement. Importantly, 13_A2 isolates carry intact and in planta induced Avrblb1, Avrblb2 and Avrvnt1 effector genes that trigger resistance in potato lines carrying the corresponding R immune receptor genes Rpi-blb1, Rpi-blb2, and Rpi-vnt1.1. These findings point towards a strategy for deploying genetic resistance to mitigate the impact of the 13_A2 lineage and illustrate how pathogen population monitoring, combined with genome analysis, informs the management of devastating disease epidemic

Overtourism

In the past two decades, significant public investments in cultural infrastructure and events encouraged the private sector to consider new investment opportunities in Valletta, particularly in short-term rental accommodation, catering establishments and boutique hotels. In recent years, there was a sharp increase in boutique hotels, tourism rentals and catering establishments. Increased tourism activity reduced liveability for Valletta residents. The research finds that there are the initial signs of overtourism and that this is a source of concern, mainly to Valletta residents and to persons with an interest in urban heritage. If no action is taken to mitigate, it is likely that some of the negative impacts will become severe and unacceptable.peer-reviewe

Terrain, politics, history

This article is based on the 2019 Dialogues in Human Geography plenary lecture at the Royal Geographical Society. It has four parts. The first discusses my work on territory in relation to recent work by geographers and others on the vertical, the volumetric, the voluminous, and the milieu as ways of thinking space in three-dimensions, of a fluid and dynamic earth. Second, it proposes using the concept of terrain to analyse the political materiality of territory. Third, it adds some cautions to this, through thinking about the history of the concept of terrain in geographical thought, which has tended to associate it with either physical or military geography. Finally, it suggests that this work is a way geographers might begin to respond to the challenge recently made by Bruno Latour, where he suggests that ‘belonging to a territory is the phenomenon most in need of rethinking and careful redescription; learning new ways to inhabit the Earth is our biggest challenge’. Responding to Latour continues this thinking about the relations between territory, Earth, land, and ground, and their limits

Identification and thermochemical analysis of high-lignin feedstocks for biofuel and biochemical production

Background - Lignin is a highly abundant biopolymer synthesized by plants as a complex component of plant secondary cell walls. Efforts to utilize lignin-based bioproducts are needed. Results - Herein we identify and characterize the composition and pyrolytic deconstruction characteristics of high-lignin feedstocks. Feedstocks displaying the highest levels of lignin were identified as drupe endocarp biomass arising as agricultural waste from horticultural crops. By performing pyrolysis coupled to gas chromatography-mass spectrometry, we characterized lignin-derived deconstruction products from endocarp biomass and compared these with switchgrass. By comparing individual pyrolytic products, we document higher amounts of acetic acid, 1-hydroxy-2-propanone, acetone and furfural in switchgrass compared to endocarp tissue, which is consistent with high holocellulose relative to lignin. By contrast, greater yields of lignin-based pyrolytic products such as phenol, 2-methoxyphenol, 2-methylphenol, 2-methoxy-4-methylphenol and 4-ethyl-2-methoxyphenol arising from drupe endocarp tissue are documented. Conclusions - Differences in product yield, thermal decomposition rates and molecular species distribution among the feedstocks illustrate the potential of high-lignin endocarp feedstocks to generate valuable chemicals by thermochemical deconstruction

Lifestyle, efficiency and limits: modelling transport energy and emissions using a socio-technical approach

It is well-known that societal energy consumption and pollutant emissions from transport are influenced not only by technical efficiency, mode choice and the carbon/pollutant content of energy but also by lifestyle choices and socio-cultural factors. However, only a few attempts have been made to integrate all of these insights into systems models of future transport energy demand or even scenario analysis. This paper addresses this gap in research and practice by presenting the development and use of quantitative scenarios using an integrated transport-energy-environment systems model to explore four contrasting futures for Scotland that compare transport-related ‘lifestyle’ changes and socio-cultural factors against a transition pathway focussing on transport electrification and the phasing out of conventionally fuelled vehicles using a socio-technical approach. We found that radical demand and supply strategies can have important synergies and trade-offs between reducing life cycle greenhouse gas and air quality emissions. Lifestyle change alone can have a comparable and earlier effect on transport carbon and air quality emissions than a transition to EVs with no lifestyle change. Yet, the detailed modelling of four contrasting futures suggests that both strategies have limits to meeting legislated carbon budgets, which may only be achieved with a combined strategy of radical change in travel patterns, mode and vehicle choice, vehicle occupancy and on-road driving behaviour with high electrification and phasing out of conventional petrol and diesel road vehicles. The newfound urgency of ‘cleaning up our act’ since the Paris Agreement and Dieselgate scandal suggests that we cannot just wait for the ‘technology fix’

Antiinflammatory Therapy with Canakinumab for Atherosclerotic Disease

Background: Experimental and clinical data suggest that reducing inflammation without affecting lipid levels may reduce the risk of cardiovascular disease. Yet, the inflammatory hypothesis of atherothrombosis has remained unproved. Methods: We conducted a randomized, double-blind trial of canakinumab, a therapeutic monoclonal antibody targeting interleukin-1β, involving 10,061 patients with previous myocardial infarction and a high-sensitivity C-reactive protein level of 2 mg or more per liter. The trial compared three doses of canakinumab (50 mg, 150 mg, and 300 mg, administered subcutaneously every 3 months) with placebo. The primary efficacy end point was nonfatal myocardial infarction, nonfatal stroke, or cardiovascular death. RESULTS: At 48 months, the median reduction from baseline in the high-sensitivity C-reactive protein level was 26 percentage points greater in the group that received the 50-mg dose of canakinumab, 37 percentage points greater in the 150-mg group, and 41 percentage points greater in the 300-mg group than in the placebo group. Canakinumab did not reduce lipid levels from baseline. At a median follow-up of 3.7 years, the incidence rate for the primary end point was 4.50 events per 100 person-years in the placebo group, 4.11 events per 100 person-years in the 50-mg group, 3.86 events per 100 person-years in the 150-mg group, and 3.90 events per 100 person-years in the 300-mg group. The hazard ratios as compared with placebo were as follows: in the 50-mg group, 0.93 (95% confidence interval [CI], 0.80 to 1.07; P = 0.30); in the 150-mg group, 0.85 (95% CI, 0.74 to 0.98; P = 0.021); and in the 300-mg group, 0.86 (95% CI, 0.75 to 0.99; P = 0.031). The 150-mg dose, but not the other doses, met the prespecified multiplicity-adjusted threshold for statistical significance for the primary end point and the secondary end point that additionally included hospitalization for unstable angina that led to urgent revascularization (hazard ratio vs. placebo, 0.83; 95% CI, 0.73 to 0.95; P = 0.005). Canakinumab was associated with a higher incidence of fatal infection than was placebo. There was no significant difference in all-cause mortality (hazard ratio for all canakinumab doses vs. placebo, 0.94; 95% CI, 0.83 to 1.06; P = 0.31). Conclusions: Antiinflammatory therapy targeting the interleukin-1β innate immunity pathway with canakinumab at a dose of 150 mg every 3 months led to a significantly lower rate of recurrent cardiovascular events than placebo, independent of lipid-level lowering. (Funded by Novartis; CANTOS ClinicalTrials.gov number, NCT01327846.