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A family of symmetrical and unsymmetrical aza-dipyrromethenes and aza-BODIPYs with through-bond and face-to-face π-interaction between termini
No full textThe dipyrromethenes (DPMs) and their borylated adducts (BODIPYs) constitute a class of versatile chromophores that has become one of the most widely studied over recent decades. They combine excellent photochemistry properties with opportunity for synthetic manipulation and tuning. We report here a related class of aza-dibenzodipyrromethenes and show that they present an interesting architecture where the core adopts a helical arrangement that places terminal aryl functional groups directly on top of each other in close, π-stacked arrangement. Complexation by reaction with boron trifluoride, demonstrated to be significantly improved by addition of trimethylsilyl chloride, induces a stereochemical inversion that destroys the helix, flattens the system, and switches on fluorescence. A wide range of terminal aromatic fragments can be easily introduced. Unsymmetrical derivatives can be made conveniently by simple mixed condensations, but a controlled, rational approach is also described whereby the ability of one component to homocondense (the more reactive partner) is removed by conversion to its corresponding tosylate or triflate. The two approaches have been investigated through successful introduction of complementary electron rich, electron poor, and π-extended functional termini.</p
Hospitalisation and mortality before and during the COVID-19 pandemic in individuals with cardiorenal–metabolic diseases in the UK: a retrospective cohort study
No full textBackground: health-care access and use were considerably disrupted during the COVID-19 pandemic. This study assessed the sex-specific effect of the pandemic on hospitalisations and mortality among individuals in England with type 2 diabetes, cardiovascular disease, and chronic kidney disease.Methods: we conducted a retrospective cohort study using the UK Clinical Practice Research Datalink (CPRD) GOLD primary care database in individuals with data linkage available to the Hospital Episode Statistics Admitted Patient Care (HES APC), the Office for National Statistics (ONS) death registry, and the patient-level Index of Multiple Deprivation (IMD) 2019. Individuals were eligible for inclusion if they were registered in CPRD GOLD on the study start date (ie, March 1, 2017); were aged 18 years or older; had up-to-standard registration in CPRD GOLD for at least 1 year before the study start date; and had linkage available to HES APC, ONS, and IMD data. Adults with type 2 diabetes, cardiovascular disease, or chronic kidney disease were identified and followed up for 2 years before (March 1, 2018, to Feb 29, 2020) and 1 year during (March 1, 2020, to Feb 28, 2021) the COVID-19 pandemic. We estimated sex-specific crude incidence rates of all-cause hospitalisations and mortality in both periods. We also estimated sex-stratified, age-adjusted incidence rate ratios (IRRs) for all-cause hospitalisations and mortality during March 1, 2020, to Feb 28, 2021 versus March 1, 2018, to Feb 29, 2020 using Poisson models. Excess deaths were estimated by comparing observed and expected mortality rates.Findings: among 769 551 eligible individuals, 59 169 (7·7%) had type 2 diabetes, 49 754 (6·5%) had cardiovascular disease, and 39 803 (5·2%) had chronic kidney disease in 2018. From 2018–20 to 2020–21, all-cause hospitalisations declined across all disease cohorts, with the largest reduction observed in female participants with type 2 diabetes (from 568 [95% CI 561–575] to 394 [384–404] events per 1000 person-years; adjusted IRR [aIRR] 0·71 [95% CI 0·69–0·73]). From 2018–20 to 2020–21, all-cause mortality increased in all three cohorts and was highest among male participants (from 62 [95% CI 59–65] to 77 [71–83] events per 1000 person-years; aIRR 1·25 [95% CI 1·14–1·38]) and female participants (from 54 [95% CI 52–57] to 73 [67–79] events per 1000 person-years; aIRR 1·36 [95% CI 1·23–1·49]) with chronic kidney disease. In 2020 in England, there were approximately 24 500, 37 300, and 38 000 excess deaths in individuals with type 2 diabetes, cardiovascular disease, and chronic kidney disease, respectively.Interpretation: these findings show the effect of COVID-19 on male and female participants with three common chronic conditions in England. Prioritising care for groups at increased risk of severe outcomes and improving resilience are crucial for ensuring continuity of care during future public health crises.Funding: Health Data Research UK, ONS, and UK Research and Innovation.<br/
Flow-acoustic resonance in deep and inclined cavities
No full textThis paper presents numerical investigations of flow-acoustic resonances in deep and inclined cavities using wall-resolved large-eddy simulations. The study is based on a fixed aspect ratio of D/L = 2.632, subjected to two Mach numbers of 0.2 and 0.3 (with the focus on the latter) at three different angles of inclination (α = 30◦, 60◦, and 90◦). Fully turbulent boundary layers generated from independent precursor simulations are employed upstream of the cavities. The simulation results show significant differences in aeroacoustic response between inclined and orthogonal cavities, particularly at M∞ = 0.3, where the inclined cavities exhibit stronger resonances (by more than a 20 dB) at a lower peak frequency (St = 0.276) compared to that of the orthogonal cavity, which occurred at St = 0.849. Acoustic modal analysis identifies these frequencies as the 1st and 2nd eigenmodes, respectively. Further analysis shows that the disparity in mode selection between the orthogonal and inclined cavities is linked with the hydrodynamic modes (vortex dynamics) that pair with the acoustic modes. In the orthogonal cavity, a 2nd hydrodynamic mode prevailed where two relatively small vortices were travelling across the cavity opening simultaneously. In the inclined cavities, however, a single large-scale roll-up vortex, a 1st hydrodynamics mode, is generated in relation with strong Kelvin-Helmholtz instability in the shear layer. More importantly, the vortex spends a substantial amount of its lifetime growing in size without travelling downstream rapidly. This results in a longer crossing time per cycle which correlates with the 1st acoustic eigenmode frequency (St = 0.276). In addition, an aeroacoustic resolvent analysis indicates that inclined cavities amplify acoustic responses more effectively and exhibit weaker source-sink cancellations than the orthogonal cavity. These mechanisms are identified as the primary contributors to the enhanced aeroacoustic responses in the inclined cavities. Finally, it is proposed that the ratio between acoustic particle displacement and momentum thicknesses may be used as a criterion to predict the onset of deep cavity resonance with the distinctive vortex dynamics identified in this paper
Clinical guidelines and other guidance from the European Association for the Study of Diabetes (EASD)
No full textMapping lesbians’ everyday community-making in a small city: (in)visibility, belonging and safety
No full textThis paper presents findings from a project exploring how lesbians make community in the ‘ordinary city’ of Southampton on the South coast of England. In the context of trans-exclusionary debates and the supposed demise of lesbian spaces, we sought to discover how self-identified lesbian people in Southampton conceptualised the location and boundaries of their community, The study used collaborative participatory mapping techniques, which resulted in a diffuse and multi-layered understanding of lesbian community in the city. The paper focuses on three key themes: (1) crafting ‘safe’ spaces; (2) terminology: naming ‘lesbians’ and (3) finding and creating places of community. The paper concludes that finding a space to articulate an explicitly lesbian identity can be fraught, but is deeply valued, continually becoming, and carefully negotiated both between peers and within urban space. Collaborative mapping is shown as a valuable tool in delivering more inclusive participatory research that can help foster transformative and emancipatory research into LGBTQ communities and spaces
It’s a three-ring circus: how morally educative practices are undermined by institutions
No full textSince the publication of Alasdair MacIntyre’s After Virtue in 1981, tensions inherent to the relationship between morally educative practices and the institutions that house them have been widely noted. We propose a taxonomy of the ways in which the pursuit of external goods by institutions undermines the pursuit of the internal goods of practices. These comprise substitution, where the institution replaces the pursuit of one type of good by another; frustration, where opportunities for practitioners to discover goods or develop new standards of excellence are frustrated by institutional priorities and resource allocation; and injustice, which undermines the integrity of relationships within the organization and/or with partners. These threats, though analytically distinct, are often mutually reinforcing. This conceptual contribution is illustrated both by the extant literature and by a novel context, the three-ring circus
On the multiphoton ionisation photoelectron spectra of phenol
No full textThe phenol molecule is a prototype for non-adiabatic dynamics and the excited-state photochemistry of biomolecules. In this article, we report a joint theoretical and experimental investigation on the resonance enhanced multiphoton ionisation photoelectron (REMPI) spectra of the two lowest ionisation bands of phenol. The focus is on the theoretical interpretation of the measured spectra using quantum dynamics simulations. These were performed by numerically solving the time-dependent Schrödinger equation using the multi-layer variant of the multiconfiguration time-dependent Hartree algorithm together with a vibronic coupling Hamiltonian model. The ionising laser pulse is modelled explicitly within the ionisation continuum model to simulate experimental femtosecond 1+1 REMPI photoelectron spectra. These measured spectra are sensitive to very short lived electronically excited states, providing a rigorous benchmark for our theoretical methods. The match between experiment and theory allows for an interpretation of the features of the spectra at different wavelengths and shows that there are features due to both ‘direct' and ‘indirect' ionisation, resulting from non-resonant and resonant excitation by the pump pulse
The cure d’exercice: understanding the therapeutic value of sport and physical exercise in the Paris region, c. 1880-1950
No full textThe chapter focuses on the emergence of ideas about the therapeutic nature of sport and physical exercise in early to mid-twentieth-century France. It argues that the medicalization of physical education in the years after the First World War was both cause and effect of the conviction that physical movement would improve individual and national health. Public authorities and private associations were equally invested through mid-century in the 'exercise cure' as an effective remedy for tuberculosis, the effects of poor living conditions, and in some quarters the decline of the 'race'. Yet this investment cannot be reduced to a eugenicist commitment to social hygiene. It also speaks to the purchase of medical naturism, and to a widespread if diffuse commitment to addressing emotional health through the power of an imagined mind-body connection. Exploring the deployment of the ‘exercise cure’ in open-air schools and a civic association from the 1920s to the post-1945 years, the chapter ultimately sheds light on the emergence of wellbeing as a category of experience and analysis
Masculinity, trauma, and armed conflict: how gender norms shape and perpetuate trauma among men
No full textSelf-awareness and personhood in non-human animals
No full textBeyond simple consciousness or sentience, some nonhuman animals may possess more sophisticated cognitive abilities linked to capacities for self-awareness or even personhood; capacities that may influence our attitudes toward the importance of their suffering. In this chapter we first examine the concepts of consciousness, suffering, self-awareness and personhood, before surveying the current evidence for these capacities in different animal species and discussing their relevance to the moral importance of animal suffering. We argue that while self-awareness is not necessary for morally relevant suffering, it may serve to expand the range of ways in which an individual can suffer (including increasing the harm of death), as well as potentially grounding a higher level of moral status
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