Bridging the gap: viable reaction pathways from tetrahedrane to benzyne.

The addition of sp-carbon-containing molecules to polycyclic sp3 tetrahedrane (c-C4H4) results in the formation of both o-benzyne (c-C6H4) and benzene (c-C6H6). Since both c-C6H4 and c-C6H6 have been detected in the interstellar medium (ISM), providing additional pathways for their possible astrochemical formation mechanisms can lead to the discovery of other molecules, such as c-C4H4, benzvalyne, and vinylidene (:CCH2). Addition of diatomic carbon (C2), the ethynyl radical (C2H), vinylidene, and acetylene (HCCH) to c-C4H4 is undertaken in individual pathways through high-level quantum chemical computations at the CCSD(T)-F12b/cc-pVTZ-F12 level of theory. The resulting C2 addition pathway proceeds barrierlessly through benzvalyne as an intermediate and reaches a true minimum at c-C6H4, but no leaving groups are produced which is required to dissipate excess energy within an interstellar chemical scheme. Similarly, the C2H addition to c-C4H4 produces benzvalyne as well as its related isomers. This pathway allows for the loss of a hydrogen leaving group to dissipate the resulting energy. Lastly, the HCCH and :CCH2 addition pathways follow through both benzvalene and benzvalyne in order to reach c-C6H6 (benzene) and c-C6H4 (o-benzyne) as well as H2 as the required leaving group. Although there is a barrier to the HCCH addition, the :CCH2 addition presents the contrary with only submerged barriers. These proposed mechanisms provide alternative possibilities for the formation of complex organic molecules in space.

Drivers of natural gas use in U.S. residential buildings.

Natural gas is the primary fuel used in U.S. residences, yet little is known about its consumption patterns and drivers. We use daily county-level gas consumption data to assess the spatial patterns of the relationships and the sensitivities of gas consumption to outdoor air temperature across U.S. households. We fitted linear-plus-plateau functions to daily gas consumption data in 1000 counties, and derived two key coefficients: the heating temperature threshold (Tcrit) and the gas consumption rate change per 1°C temperature drop (Slope). We identified the main predictors of Tcrit and Slope (like income, employment rate, and building type) using interpretable machine learning models built on census data. Finally, we estimated a potential 2.47 million MtCO2 annual emission reduction in U.S. residences by gas savings due to household insulation improvements and hypothetical behavioral change toward reduced consumption by adopting a 1°C lower Tcrit than the current value.

Prevalence of Antimicrobial Resistance in Escherichia coli and Salmonella Species Isolates from Chickens in Live Bird Markets and Boot Swabs from Layer Farms in Timor-Leste.

The rapid emergence of antimicrobial resistance is a global concern, and high levels of resistance have been detected in chicken populations worldwide. The purpose of this study was to determine the prevalence of antimicrobial resistance in Escherichia coli and Salmonella spp. isolated from healthy chickens in Timor-Leste. Through a cross-sectional study, cloacal swabs and boot swabs were collected from 25 live bird markets and two layer farms respectively. E. coli and Salmonella spp. from these samples were tested for susceptibility to six antimicrobials using a disk diffusion test, and a subset was tested for susceptibility to 27 antimicrobials using broth-based microdilution. E. coli and Salmonella spp. isolates showed the highest resistance towards either tetracycline or ampicillin on the disk diffusion test. E. coli from layer farms (odds ratio:5.2; 95%CI 2.0-13.1) and broilers (odds ratio:18.1; 95%CI 5.3-61.2) were more likely to be multi-drug resistant than those from local chickens. Based on the broth-based microdilution test, resistance to antimicrobials in the Timor-Leste Antimicrobial Guidelines for humans were low, except for resistance to ciprofloxacin in Salmonella spp. (47.1%). Colistin resistance in E. coli was 6.6%. Although this study shows that antimicrobial resistance in chickens was generally low in Timor-Leste, there should be ongoing monitoring in commercial chickens as industry growth might be accompanied with increased antimicrobial use.

From soap bubbles to multicellular organisms: Unraveling the role of cell adhesion and physical constraints in tile pattern formation and tissue morphogenesis.

Tile patterns, in which numerous cells are arranged in a regular pattern, are found in a variety of multicellular organisms and play important functional roles. Such regular arrangements of cells are regulated by various cell adhesion molecules. On the other hand, cell shape is also known to be regulated by physical constraints similar to those of soap bubbles. In particular, circumference minimization plays an important role, and cell adhesion negatively affects this process, thereby regulating tissue morphogenesis based on physical properties. Here, we focus on the Drosophila compound eye and the mouse auditory epithelium, and summarize the mechanisms of tile pattern formation by cell adhesion molecules such as cadherins, Irre Cell Recognition Modules (IRMs), and nectins. Phenomena that cannot be explained by physical stability based on cortical tension alone have been reported in the tile pattern formation in the compound eye, suggesting that previously unexplored forces such as cellular concentric expansion force may play an important role. We would like to summarize perspectives for future research on the mechanisms of tissue morphogenesis.

The global mismatch between equitable carbon dioxide removal liability and capacity.

Limiting climate change to 1.5°C and achieving net-zero emissions would entail substantial carbon dioxide removal (CDR) from the atmosphere by the mid-century, but how much CDR is needed at country level over time is unclear. The purpose of this paper is to provide a detailed description of when and how much CDR is required at country level in order to achieve 1.5°C and how much CDR countries can carry out domestically. We allocate global CDR pathways among 170 countries according to 6 equity principles and assess these allocations with respect to countries' biophysical and geophysical capacity to deploy CDR. Allocating global CDR to countries based on these principles suggests that CDR will, on average, represent ∼4% of nations' total emissions in 2030, rising to ∼17% in 2040. Moreover, equitable allocations of CDR, in many cases, exceed implied land and carbon storage capacities. We estimate ∼15% of countries (25) would have insufficient land to contribute an equitable share of global CDR, and ∼40% of countries (71) would have insufficient geological storage capacity. Unless more diverse CDR technologies are developed, the mismatch between CDR liabilities and land-based CDR capacities will lead to global demand for six GtCO2 carbon credits from 2020 to 2050. This demonstrates an imperative demand for international carbon trading of CDR.

Climate warming increases extreme daily wildfire growth risk in California.

California has experienced enhanced extreme wildfire behaviour in recent years1-3, leading to substantial loss of life and property4,5. Some portion of the change in wildfire behaviour is attributable to anthropogenic climate warming, but formally quantifying this contribution is difficult because of numerous confounding factors6,7 and because wildfires are below the grid scale of global climate models. Here we use machine learning to quantify empirical relationships between temperature (as well as the influence of temperature on aridity) and the risk of extreme daily wildfire growth (>10,000 acres) in California and find that the influence of temperature on the risk is primarily mediated through its influence on fuel moisture. We use the uncovered relationships to estimate the changes in extreme daily wildfire growth risk under anthropogenic warming by subjecting historical fires from 2003 to 2020 to differing background climatological temperatures and aridity conditions. We find that the influence of anthropogenic warming on the risk of extreme daily wildfire growth varies appreciably on a fire-by-fire and day-by-day basis, depending on whether or not climate warming pushes conditions over certain thresholds of aridity, such as 1.5 kPa of vapour-pressure deficit and 10% dead fuel moisture. So far, anthropogenic warming has enhanced the aggregate expected frequency of extreme daily wildfire growth by 25% (5-95 range of 14-36%), on average, relative to preindustrial conditions. But for some fires, there was approximately no change, and for other fires, the enhancement has been as much as 461%. When historical fires are subjected to a range of projected end-of-century conditions, the aggregate expected frequency of extreme daily wildfire growth events increases by 59% (5-95 range of 47-71%) under a low SSP1-2.6 emissions scenario compared with an increase of 172% (5-95 range of 156-188%) under a very high SSP5-8.5 emissions scenario, relative to preindustrial conditions.

The genomic and cellular basis of biosynthetic innovation in rove beetles.

How evolution at the cellular level potentiates change at the macroevolutionary level is a major question in evolutionary biology. With >66,000 described species, rove beetles (Staphylinidae) comprise the largest metazoan family. Their exceptional radiation has been coupled to pervasive biosynthetic innovation whereby numerous lineages bear defensive glands with diverse chemistries. Here, we combine comparative genomic and single-cell transcriptomic data from across the largest rove beetle clade, Aleocharinae. We retrace the functional evolution of two novel secretory cell types that together comprise the tergal gland-a putative catalyst behind Aleocharinae's megadiversity. We identify key genomic contingencies that were critical to the assembly of each cell type and their organ-level partnership in manufacturing the beetle's defensive secretion. This process hinged on evolving a mechanism for regulated production of noxious benzoquinones that appears convergent with plant toxin release systems, and synthesis of an effective benzoquinone solvent that weaponized the total secretion. We show that this cooperative biosynthetic system arose at the Jurassic-Cretaceous boundary, and that following its establishment, both cell types underwent ∼150 million years of stasis, their chemistry and core molecular architecture maintained almost clade-wide as Aleocharinae radiated globally into tens of thousands of lineages. Despite this deep conservation, we show that the two cell types have acted as substrates for the emergence of adaptive, biochemical novelties-most dramatically in symbiotic lineages that have infiltrated social insect colonies and produce host behavior-manipulating secretions. Our findings uncover genomic and cell type evolutionary processes underlying the origin, functional conservation and evolvability of a chemical innovation in beetles.

Nitrogen fixation in the stag beetle, Ceruchus piceus (Coleoptera: Lucanidae): could insects contribute more to ecosystem nitrogen budgets than previously thought?

Nitrogen (N) is a key nutrient required by all living organisms for growth and development, but is a limiting resource for many organisms. Organisms that feed on material with low N content, such as wood, might be particularly prone to N limitation. In this study, we investigated the degree to which the xylophagous larvae of the stag beetle Ceruchus piceus (Weber) use associations with N-fixing bacteria to acquire N. We paired acetylene reduction assays by cavity ring-down absorption spectroscopy (ARACAS) with 15N2 incubations to characterize rates of N fixation within C. piceus. Not only did we detect significant N fixation activity within C. piceus larvae, but we calculated a rate that was substantially higher than most previous reports for N fixation in insects. While taking these measurements, we discovered that N fixation within C. piceus can decline rapidly in a lab setting. Consequently, our results demonstrate that previous studies, which commonly keep insects in the lab for long periods of time prior to and during measurement, may have systematically under-reported rates of N fixation in insects. This suggests that within-insect N fixation may contribute more to insect nutrition and ecosystem-scale N budgets than previously thought.

Rebound effects could offset more than half of avoided food loss and waste.

Reducing food loss and waste (FLW) could lessen the environmental impacts of food systems and improve food security. However, rebound effects-whereby efficiency improvements cause price decreases and consumption increases-may offset some avoided FLW. Here we model rebounds in food consumption under a scenario of costless FLW reduction. We project that consumption rebound could offset 53-71% of avoided FLW. Such rebounds would imply similar percentage reductions in environmental benefits (carbon emissions, land use, water use) and improvements in food security benefits (increased calorie availability), highlighting a tension between these two objectives. Evidence from energy systems suggests that indirect effects not included in our analysis could further increase rebounds. However, costs of reducing FLW would reduce rebounds. Rebound effects are therefore important to consider in efforts aimed at reducing FLW.

Carbon Monitor Europe near-real-time daily CO2 emissions for 27 EU countries and the United Kingdom.

With the urgent need to implement the EU countries pledges and to monitor the effectiveness of Green Deal plan, Monitoring Reporting and Verification tools are needed to track how emissions are changing for all the sectors. Current official inventories only provide annual estimates of national CO2 emissions with a lag of 1+ year which do not capture the variations of emissions due to recent shocks including COVID lockdowns and economic rebounds, war in Ukraine. Here we present a near-real-time country-level dataset of daily fossil fuel and cement emissions from January 2019 through December 2021 for 27 EU countries and UK, which called Carbon Monitor Europe. The data are calculated separately for six sectors: power, industry, ground transportation, domestic aviation, international aviation and residential. Daily CO2 emissions are estimated from a large set of activity data compiled from different sources. The goal of this dataset is to improve the timeliness and temporal resolution of emissions for European countries, to inform the public and decision makers about current emissions changes in Europe.

Approach to anisocoria in the emergency department.

Anisocoria describes asymmetric pupillary diameter, which can result from traumatic, pharmacologic, inflammatory, or ischemic effects on the eye. In many cases, anisocoria represents a normal physiologic variant. Morbidity associated with anisocoria is directly related to the inciting cause and can vary from benign to life-threatening. A thorough understanding by emergency physicians of normal ocular neuroanatomy, and of common causes of pathologic anisocoria, including medication-induced anisocoria, can facilitate appropriate resource utilization and timely subspecialty consultation, and can help prevent irreversible ocular injury and patient morbidity. We describe a patient who presented to the emergency department with acute onset of blurry vision with anisocoria.

Angiotensin II-Mediated Neuroinflammation in the Hippocampus Contributes to Neuronal Deficits and Cognitive Impairment in Heart Failure Rats.

BACKGROUND: Heart failure (HF) is a debilitating disease affecting >64 million people worldwide. In addition to impaired cardiovascular performance and associated systemic complications, most patients with HF suffer from depression and substantial cognitive decline. Although neuroinflammation and brain hypoperfusion occur in humans and rodents with HF, the underlying neuronal substrates, mechanisms, and their relative contribution to cognitive deficits in HF remains unknown. METHODS: To address this critical gap in our knowledge, we used a well-established HF rat model that mimics clinical outcomes observed in the human population, along with a multidisciplinary approach combining behavioral, electrophysiological, neuroanatomical, molecular and systemic physiological approaches. RESULTS: Our studies support neuroinflammation, hypoperfusion/hypoxia, and neuronal deficits in the hippocampus of HF rats, which correlated with the progression and severity of the disease. An increased expression of AT1aRs (Ang II [angiotensin II] receptor type 1a) in hippocampal microglia preceded the onset of neuroinflammation. Importantly, blockade of AT1Rs with a clinically used therapeutic drug (Losartan), and delivered in a clinically relevant manner, efficiently reversed neuroinflammatory end points (but not hypoxia ones), resulting in turn in improved cognitive performance in HF rats. Finally, we show than circulating Ang II can leak and access the hippocampal parenchyma in HF rats, constituting a possible source of Ang II initiating the neuroinflammatory signaling cascade in HF. CONCLUSIONS: In this study, we identified a neuronal substrate (hippocampus), a mechanism (Ang II-driven neuroinflammation) and a potential neuroprotective therapeutic target (AT1aRs) for the treatment of cognitive deficits in HF.

CarbonMonitor-Power near-real-time monitoring of global power generation on hourly to daily scales.

We constructed a frequently updated, near-real-time global power generation dataset: CarbonMonitor-Power since January, 2016 at national levels with near-global coverage and hourly-to-daily time resolution. The data presented here are collected from 37 countries across all continents for eight source groups, including three types of fossil sources (coal, gas, and oil), nuclear energy and four groups of renewable energy sources (solar energy, wind energy, hydro energy and other renewables including biomass, geothermal, etc.). The global near-real-time power dataset shows the dynamics of the global power system, including its hourly, daily, weekly and seasonal patterns as influenced by daily periodical activities, weekends, seasonal cycles, regular and irregular events (i.e., holidays) and extreme events (i.e., the COVID-19 pandemic). The CarbonMonitor-Power dataset reveals that the COVID-19 pandemic caused strong disruptions in some countries (i.e., China and India), leading to a temporary or long-lasting shift to low carbon intensity, while it had only little impact in some other countries (i.e., Australia). This dataset offers a large range of opportunities for power-related scientific research and policy-making.

Record-high CO2 emissions from boreal fires in 2021.

Extreme wildfires are becoming more common and increasingly affecting Earth's climate. Wildfires in boreal forests have attracted much less attention than those in tropical forests, although boreal forests are one of the most extensive biomes on Earth and are experiencing the fastest warming. We used a satellite-based atmospheric inversion system to monitor fire emissions in boreal forests. Wildfires are rapidly expanding into boreal forests with emerging warmer and drier fire seasons. Boreal fires, typically accounting for 10% of global fire carbon dioxide emissions, contributed 23% (0.48 billion metric tons of carbon) in 2021, by far the highest fraction since 2000. 2021 was an abnormal year because North American and Eurasian boreal forests synchronously experienced their greatest water deficit. Increasing numbers of extreme boreal fires and stronger climate-fire feedbacks challenge climate mitigation efforts.

Kinetics of Metastable Argon Optical Excitation and Gain in Ar/He Microplasmas.

The optically pumped rare-gas metastable laser is capable of high-intensity lasing on a broad range of near-infrared transitions for excited-state rare gas atoms (Ar*, Kr*, Ne*, Xe*) diluted in flowing He. The lasing action is generated by photoexcitation of the metastable atom to an upper state, followed by collisional energy transfer with He to a neighboring state and lasing back to the metastable state. The metastables are generated in a high-efficiency electric discharge at pressures of ∼0.4 to 1 atm. The diode-pumped rare-gas laser (DPRGL) is a chemically inert analogue to diode-pumped alkali laser (DPAL) systems, with similar optical and power scaling characteristics for high-energy laser applications. We used a continuous-wave linear microplasma array in Ar/He mixtures to produce Ar(1s5) (Paschen notation) metastables at number densities exceeding 1013 cm-3. The gain medium was optically pumped by both a narrow-line 1 W titanium-sapphire laser and a 30 W diode laser. Tunable diode laser absorption and gain spectroscopy determined Ar(1s5) number densities and small-signal gains up to ∼2.5 cm-1. Continuous-wave lasing was observed using the diode pump laser. The results were analyzed with a steady-state kinetics model relating the gain and the Ar(1s5) number density.

Smoke-weather interaction affects extreme wildfires in diverse coastal regions.

Extreme wildfires threaten human lives, air quality, and ecosystems. Meteorology plays a vital role in wildfire behaviors, and the links between wildfires and climate have been widely studied. However, it is not fully clear how fire-weather feedback affects short-term wildfire variability, which undermines our ability to mitigate fire disasters. Here, we show the primacy of synoptic-scale feedback in driving extreme fires in Mediterranean and monsoon climate regimes in the West Coast of the United States and Southeastern Asia. We found that radiative effects of smoke aerosols can modify near-surface wind, air dryness, and rainfall and thus worsen air pollution by enhancing fire emissions and weakening dispersion. The intricate interactions among wildfires, smoke, and weather form a positive feedback loop that substantially increases air pollution exposure.

Near-real-time global gridded daily CO2 emissions 2021.

We present a near-real-time global gridded daily CO2 emissions dataset (GRACED) throughout 2021. GRACED provides gridded CO2 emissions at a 0.1° × 0.1° spatial resolution and 1-day temporal resolution from cement production and fossil fuel combustion over seven sectors, including industry, power, residential consumption, ground transportation, international aviation, domestic aviation, and international shipping. GRACED is prepared from the near-real-time daily national CO2 emissions estimates (Carbon Monitor), multi-source spatial activity data emissions and satellite NO2 data for time variations of those spatial activity data. GRACED provides the most timely overview of emissions distribution changes, which enables more accurate and timely identification of when and where fossil CO2 emissions have rebounded and decreased. Uncertainty analysis of GRACED gives a grid-level two-sigma uncertainty of value of ±19.9% in 2021, indicating the reliability of GRACED was not sacrificed for the sake of higher spatiotemporal resolution that GRACED provides. Continuing to update GRACED in a timely manner could help policymakers monitor energy and climate policies' effectiveness and make adjustments quickly.