^(13)C, ^1H, and ^2H NMR Observation of Trideuterated Cyclopropylmethyl-Cyclobutyl Carbocation: A Configurationally Stable Species

With the increasing power and sophistication of experimental and theoretical methods for assigning chemical structures, it seems almost incredible that the structure of any reasonably stable organic entity with a small number of carbons could remain enigmatic for very long. Nonetheless, this is true of C_4H_7^+-one of the first "nonclassical" cations to be discovered, which has some of the characteristics expected for a very rapidly equilibrating mixture of classical cyclopropylmethyl, cyclobutyl, and 3-butenyl cations and yet other characteristics which wholly belie any description that implies conventional charge distributions or geometries derived from structural representations using solid lines representing two-electron bonds

Variations in Atmospheric CO2CO_2 Mixing Ratios across a Boston, MA Urban to Rural Gradient

Urban areas are directly or indirectly responsible for the majority of anthropogenic $CO_2$ emissions. In this study, we characterize observed atmospheric $CO_2$ mixing ratios and estimated $CO_2$ fluxes at three sites across an urban-to-rural gradient in Boston, MA, USA. $CO_2$ is a well-mixed greenhouse gas, but we found significant differences across this gradient in how, where, and when it was exchanged. Total anthropogenic emissions were estimated from an emissions inventory and ranged from $1.5 to 37.3 mg·C·ha^{-1}·yr^{-1}$ between rural Harvard Forest and urban Boston. Despite this large increase in anthropogenic emissions, the mean annual difference in atmospheric $CO_2$ between sites was approximately 5% $(20.6 \pm 0.4 ppm)$. The influence of vegetation was also visible across the gradient. Green-up occurred near day of year 126, 136, and 141 in Boston, Worcester and Harvard Forest, respectively, highlighting differences in growing season length. In Boston, gross primary production—estimated by scaling productivity by canopy cover—was ~75% lower than at Harvard Forest, yet still constituted a significant local flux of $3.8 mg·C·ha^{-1}·yr^{-1}$. In order to reduce greenhouse gas emissions, we must improve our understanding of the space-time variations and underlying drivers of urban carbon fluxes.Engineering and Applied Science

Personal traits predict conservationists’ optimism about outcomes for nature

In the face of unprecedented biodiversity loss, the belief that conservation goals can be met could play an important role in ensuring they are fulfilled. We asked conservationists how optimistic they felt about key biodiversity outcomes over the next 10 years; 2341 people familiar with conservation in 144 countries responded. Respondents expressed optimism that enabling conditions for conservation would improve but felt pressures would continue, and the state of biodiversity was unlikely to get better. Respondents with greater general optimism about life, at early-career stages, and working in practice and policy (compared to academia) reported higher conservation optimism. But most of our biodiversity and conservation status indicators were not associated with conservation optimism. Unbounded optimism without appropriate action would be misguided in the face of growing threats to biodiversity. However, supporting those struggling to see the light at the end of the tunnel could help sustain efforts to overcome these threats

Functional diversity and community assembly of river invertebrates show globally consistent responses to decreasing glacier cover

Global change threatens invertebrate biodiversity and its central role in numerous ecosystem functions and services. Functional trait analyses have been advocated to uncover global mechanisms behind biodiversity responses to environmental change, but the application of this approach for invertebrates is underdeveloped relative to other organism groups. From an evaluation of 363 records comprising >1.23 million invertebrates collected from rivers across nine biogeographic regions on three continents, consistent responses of community trait composition and diversity to replicated gradients of reduced glacier cover are demonstrated. After accounting for a systematic regional effect of latitude, the processes shaping river invertebrate functional diversity are globally consistent. Analyses nested within individual regions identified an increase in functional diversity as glacier cover decreases. Community assembly models demonstrated that dispersal limitation was the dominant process underlying these patterns, although environmental filtering was also evident in highly glacierized basins. These findings indicate that predictable mechanisms govern river invertebrate community responses to decreasing glacier cover globally.This work was funded by the following organisations: The UK Natural Environment Research Council grants and studentships GR9/2913, NE/E003729/1, NE/E004539/1, NE/E004148/1, 20 NE/G523963/1, NER/S/A/2003/11192, and NE/L002574/1; the European Union Environment and Climate Programme Arctic and Alpine Stream Ecosystem Research (AASER) project (ENV-CT95-0164); EU-FP7 Assessing Climate impacts on the Quality and quantity of WAter (ACQWA) project (212250); Icelandic Research Council (954890095, 954890096); University of Iceland Research Fund (GMG96, GMG97, GMG98), Wyoming Center for Environmental Hydrology and Geophysics-National Science Foundation (1208909); USA-Wyoming NASA Space Grant Faculty Research Initiation (#NNX10A095H); USA-NSF Wyoming Epscor; Nationalpark Hohe Tauern, Austria; the Royal Society (International Outgoing Grant 2006/R4); the Leverhulme Trust; the Universities of Leeds, Birmingham, Iceland and Innsbruck; European Centre for Arctic Environmental Research (ARCFAC): a Research Infrastructures Action of the European Community FP6 (026129-2008- 72); the Stelvio National Park (2000-2001); the Autonomous Province of Trento (HIGHEST project, 2001-2004, del. PAT n. 1060/2001; VETTA project, 2003-2006, del. PAT n. 3402/2002); MUSE-Museo delle Scienze. We are grateful to Russell Taylor and Mike Winterbourn at the University of Canterbury, NZ, who helped to collect NZ invertebrate data and assisted with identification, and to Hakon Adalsteinsson who contributed to data collection in Iceland. Many other people, too numerous to mention, assisted with fieldwork at all of the study locations. The European Science Foundation sponsored an exploratory ┘ﾗヴﾆゲｴﾗヮ WﾐデｷデﾉWS さGﾉ;IｷWヴ-fed rivers, hydroecology and climate change: current knowledge and future network of monitoring sites (GLAC-HYDROECO-NETぶざ デｴ;デ ┘;ゲ ｴWﾉS ｷﾐ Birmingham, UK in September of 2013 where some of the ideas in this paper were first discussedPeer Reviewe

CD47 plays a critical role in T-cell recruitment by regulation of LFA-1 and VLA-4 integrin adhesive functions

CD47 plays an important but incompletely understood role in the innate and adaptive immune responses. CD47, also called integrin-associated protein, has been demonstrated to associate in cis with β1 and β3 integrins. Here we test the hypothesis that CD47 regulates adhesive functions of T-cell α4β1 (VLA-4) and αLβ2 (LFA-1) in in vivo and in vitro models of inflammation. Intravital microscopy studies reveal that CD47(−/−) Th1 cells exhibit reduced interactions with wild-type (WT) inflamed cremaster muscle microvessels. Similarly, murine CD47(−/−) Th1 cells, as compared with WT, showed defects in adhesion and transmigration across tumor necrosis factor-α (TNF-α)–activated murine endothelium and in adhesion to immobilized intercellular adhesion molecule 1 (ICAM-1) and vascular cell adhesion protein 1 (VCAM-1) under flow conditions. Human Jurkat T-cells lacking CD47 also showed reduced adhesion to TNF-α–activated endothelium and ICAM-1 and VCAM-1. In cis interactions between Jurkat T-cell β2 integrins and CD47 were detected by fluorescence lifetime imaging microscopy. Unexpectedly, Jurkat CD47 null cells exhibited a striking defect in β1 and β2 integrin activation in response to Mn(2+) or Mg(2+)/ethylene glycol tetraacetic acid treatment. Our results demonstrate that CD47 associates with β2 integrins and is necessary to induce high-affinity conformations of LFA-1 and VLA-4 that recognize their endothelial cell ligands and support leukocyte adhesion and transendothelial migration

ALMA Reveals the Anatomy of the mm-sized Dust and Molecular Gas in the HD 97048 Disk

Transitional disks show a lack of excess emission at infrared wavelengths due to a large dust cavity, that is often corroborated by spatially resolved observations at ∼mm wavelengths. We present the first spatially resolved ∼ mm-wavelength images of the disk around the Herbig Ae/Be star, HD 97048. Scattered light images show that the disk extends to ≈640 au. ALMA data reveal a circular-symmetric dusty disk extending to ≈350 au, and a molecular disk traced in CO J = 3-2 emission, extending to ≈750 au. The CO emission arises from a flared layer with an opening angle ≈30°–40°. HD 97048 is another source for which the large (∼ mm-sized) dust grains are more centrally concentrated than the small (∼μm-sized) grains and molecular gas, likely due to radial drift. The images and visibility data modeling suggest a decrement in continuum emission within ≈50 au, consistent with the cavity size determined from mid-infrared imaging (34 ± 4 au). The extracted continuum intensity profiles show ring-like structures with peaks at ≈50, 150, and 300 au, with associated gaps at ≈100 and 250 au. This structure should be confirmed in higher-resolution images (FWHM ≈ 10–20 au). These data confirm the classification of HD 97048 as a transitional disk that also possesses multiple ring-like structures in the dust continuum emission. Additional data are required at multiple and well-separated frequencies to fully characterize the disk structure, and thereby constrain the mechanism(s) responsible for sculpting the HD 97048 disk

Procalcitonin Is Not a Reliable Biomarker of Bacterial Coinfection in People With Coronavirus Disease 2019 Undergoing Microbiological Investigation at the Time of Hospital Admission

Abstract Admission procalcitonin measurements and microbiology results were available for 1040 hospitalized adults with coronavirus disease 2019 (from 48 902 included in the International Severe Acute Respiratory and Emerging Infections Consortium World Health Organization Clinical Characterisation Protocol UK study). Although procalcitonin was higher in bacterial coinfection, this was neither clinically significant (median [IQR], 0.33 [0.11–1.70] ng/mL vs 0.24 [0.10–0.90] ng/mL) nor diagnostically useful (area under the receiver operating characteristic curve, 0.56 [95% confidence interval, .51–.60]).</jats:p

Implementation of corticosteroids in treating COVID-19 in the ISARIC WHO Clinical Characterisation Protocol UK:prospective observational cohort study

BACKGROUND: Dexamethasone was the first intervention proven to reduce mortality in patients with COVID-19 being treated in hospital. We aimed to evaluate the adoption of corticosteroids in the treatment of COVID-19 in the UK after the RECOVERY trial publication on June 16, 2020, and to identify discrepancies in care. METHODS: We did an audit of clinical implementation of corticosteroids in a prospective, observational, cohort study in 237 UK acute care hospitals between March 16, 2020, and April 14, 2021, restricted to patients aged 18 years or older with proven or high likelihood of COVID-19, who received supplementary oxygen. The primary outcome was administration of dexamethasone, prednisolone, hydrocortisone, or methylprednisolone. This study is registered with ISRCTN, ISRCTN66726260. FINDINGS: Between June 17, 2020, and April 14, 2021, 47 795 (75·2%) of 63 525 of patients on supplementary oxygen received corticosteroids, higher among patients requiring critical care than in those who received ward care (11 185 [86·6%] of 12 909 vs 36 415 [72·4%] of 50 278). Patients 50 years or older were significantly less likely to receive corticosteroids than those younger than 50 years (adjusted odds ratio 0·79 [95% CI 0·70–0·89], p=0·0001, for 70–79 years; 0·52 [0·46–0·58], p80 years), independent of patient demographics and illness severity. 84 (54·2%) of 155 pregnant women received corticosteroids. Rates of corticosteroid administration increased from 27·5% in the week before June 16, 2020, to 75–80% in January, 2021. INTERPRETATION: Implementation of corticosteroids into clinical practice in the UK for patients with COVID-19 has been successful, but not universal. Patients older than 70 years, independent of illness severity, chronic neurological disease, and dementia, were less likely to receive corticosteroids than those who were younger, as were pregnant women. This could reflect appropriate clinical decision making, but the possibility of inequitable access to life-saving care should be considered. FUNDING: UK National Institute for Health Research and UK Medical Research Council

2021 roadmap for sodium-ion batteries

Abstract: Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid–electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology