Dealkenylative Functionalizations: Conversion of Alkene C(sp3)-C(sp2) Bonds into C(sp3)-X Bonds via Redox-Based Radical Processes.

This review highlights the history and recent advances in dealkenylative functionalization. Through this deconstructive strategy, radical functionalizations occur under mild, robust conditions. The reactions described proceed with high efficiency, good stereoselectivity, tolerate many functional groups, and are completed within a matter of minutes. By cleaving the C(sp3)-C(sp2) bond of terpenes and terpenoid-derived precursors, rapid diversification of natural products is possible.

Negative density dependence characterizes mutualistic interactions between birds and fruiting plants across latitudes.

Negative density dependence (NDD) in biotic interactions of interference such as plant-plant competition, granivory and herbivory are well-documented mechanisms that promote species' coexistence in diverse plant communities worldwide. Here, we investigated the generality of a novel type of NDD mechanism that operates through the mutualistic interactions of frugivory and seed dispersal among fruit-eating birds and plants. By sampling community-wide frugivory interactions at high spatial and temporal resolution in Pennsylvania, Puerto Rico, Peru, Brazil and Argentina, we evaluated whether interaction frequencies between birds and fruit resources occurred more often (selection), as expected, or below expectations (under-utilization) set by the relative fruit abundance of the fruit resources of each plant species. Our models considered the influence of temporal scales of fruit availability and bird phylogeny and diets, revealing that NDD characterizes frugivory across communities. Irrespective of taxa or dietary guild, birds tended to select fruits of plant species that were proportionally rare in their communities, or that became rare following phenological fluctuations, while they mostly under-utilized abundant fruit resources. Our results demonstrate that negative density-dependence in frugivore-plant interactions provides a strong equalizing mechanism for the dispersal processes of fleshy-fruited plant species in temperate and tropical communities, likely contributing to building and sustaining plant diversity. This article is part of the theme issue 'Diversitydependence of dispersal: interspecific interactions determine spatial dynamics'.

Population Percentage and Population Size of Men Who Have Sex With Men in the United States, 2017-2021: Meta-Analysis of 5 Population-Based Surveys.

BACKGROUND: Male-to-male sexual transmission continues to account for the greatest proportion of new HIV diagnoses in the United States. However, calculating population-specific surveillance metrics for HIV and other sexually transmitted infections requires regularly updated estimates of the number and proportion of men who have sex with men (MSM) in the United States, which are not collected by census surveys. OBJECTIVE: The purpose of this analysis was to estimate the number and percentage of MSM in the United States from population-based surveys. METHODS: We used data from 5 population-based surveys to calculate weighted estimates of the proportion of MSM in the United States and pooled these estimates using meta-analytic procedures. We estimated the proportion of MSM using sexual behavior-based questions (encompassing anal or oral sex) for 3 recall periods-past 12 months, past 5 years, and lifetime. In addition, we estimated the proportion of MSM using self-reported identity and attraction survey responses. The total number of MSM and non-MSM in the United States were calculated from estimates of the percentage of MSM who reported sex with another man in the past 12 months. RESULTS: The percentage of MSM varied by recall period: 3.3% (95% CI 1.7%-4.9%) indicated sex with another male in the past 12 months, 4.7% (95% CI 0.0%-33.8%) in the past 5 years, and 6.2% (95% CI 2.9%-9.5%) in their lifetime. There were comparable percentages of men who identified as gay or bisexual (3.4%, 95% CI 2.2%-4.6%) or who indicated that they are attracted to other men (4.9%, 95% CI 3.1%-6.7%) based on pooled estimates. Our estimate of the total number of MSM in the United States is 4,230,000 (95% CI 2,179,000-6,281,000) based on the history of recent sexual behavior (sex with another man in the past 12 months). CONCLUSIONS: We calculated the pooled percentage and number of MSM in the United States from a meta-analysis of population-based surveys collected from 2017 to 2021. These estimates update and expand upon those derived from the Centers for Disease Control and Prevention in 2012 by including estimates of the percentage of MSM based on sexual identity and sexual attraction. The percentage and number of MSM in the United States is an important indicator for calculating population-specific disease rates and eligibility for preventive interventions such as pre-exposure prophylaxis.

The Association of Vaccination for Common Adult Infectious Diseases and Uptake of COVID-19 Vaccines among 5,006,851 Veterans, 20 December 2020-31 October 2021.

Disparities in vaccination coverage for coronavirus disease 2019 (COVID-19) in the United States (U.S.) are consistent barriers limiting our ability to control the spread of disease, particularly those by age and race/ethnicity. This study examines the association between previous vaccination for common adult infectious diseases and vaccination for SARS-CoV-2 among a cohort of veterans in the U.S. Sociodemographic and clinical data were utilized from three databases within the Veterans Health Administration included in the electronic health record. We examined the association of previous vaccination for common adult vaccinations through six separate multivariable logistic regression analyses, one for each previous vaccine exposure, adjusting for demographic and clinical variables. We also examined the association of receiving any one of the six common adult vaccinations and vaccination against SARS-CoV-2. Adjusted models indicate higher odds of vaccination for SARS-CoV-2 among those who received each of the previous vaccinations. Significant differences were also noted by race/ethnicity and age. Veterans who recorded receiving any one of the previous vaccinations for common adult infections had significantly greater odds of receiving any vaccination against SARS-CoV-2. Understanding veterans' previous vaccination status can assist researchers and clinicians in impacting the uptake of novel vaccines, such as vaccination against SARS-CoV-2.

When all C-C breaks LO-Ose.

Organic peroxides are becoming popular intermediates for novel chemical transformations. The weak O-O bond is readily reduced by transition metals, including iron and copper, to initiate a radical cascade process that breaks C-C bonds. Great potential exists for the rapid generation of complexity, originating from the ability to couple the resulting free radicals with a wide range of partners. First, this review article discusses the history and synthesis of organic peroxides, providing the context necessary to understand this methodology. Then, it highlights 91 examples of recent applications of the radical functionalization of C-C bonds accessed through the transition metal-mediated reduction of organic peroxides. Finally, we provide some comments about safety when working with organic peroxides.

Social contact patterns among employees in U.S. long-term care facilities during the COVID-19 pandemic, December 2020 to June 2021.

OBJECTIVE: We measured contact patterns using social contact diaries for 157 U.S. long-term care facility employees from December 2020 - June 2021. These data are crucial for analyzing mathematical transmission models and for informing healthcare setting infection control policy. RESULTS: The median number of daily contacts was 10 (IQR 8-11). Household contacts were more likely partially masked than fully masked, more likely to involve physical contact, and longer in duration compared to facility contacts.

Bison movements change with weather: Implications for their continued conservation in the Anthropocene.

Animal movement patterns are affected by complex interactions between biotic and abiotic landscape conditions, and these patterns are being altered by weather variability associated with a changing climate. Some animals, like the American plains bison (Bison bison L.; hereafter, plains bison), are considered keystone species, thus their response to weather variability may alter ecosystem structure and biodiversity patterns. Many movement studies of plains bison and other ungulates have focused on point-pattern analyses (e.g., resource-selection) that have provided information about where these animals move, but information about when or why these animals move is limited. For example, information surrounding the influence of weather on plains bison movement in response to weather is limited but has important implications for their conservation in a changing climate. To explore how movement distance is affected by weather patterns and drought, we utilized 12-min GPS data from two of the largest plains bison herds in North America to model their response to weather and drought parameters using generalized additive mixed models. Distance moved was best predicted by air temperature, wind speed, and rainfall. However, air temperature best explained the variation in distance moved compared to any other single parameter we measured, predicting a 48% decrease in movement rates above 28°C. Moreover, severe drought (as indicated by 25-cm depth soil moisture) better predicted movement distance than moderate drought. The strong influence of weather and drought on plains bison movements observed in our study suggest that shifting climate and weather will likely affect plains bison movement patterns, further complicating conservation efforts for this wide-ranging keystone species. Moreover, changes in plains bison movement patterns may have cascading effects for grassland ecosystem structure, function, and biodiversity. Plains bison and grassland conservation efforts need to be proactive and adaptive when considering the implications of a changing climate on bison movement patterns.

Next-generation technologies unlock new possibilities to track rangeland productivity and quantify multi-scale conservation outcomes.

Historically, relying on plot-level inventories impeded our ability to quantify large-scale change in plant biomass, a key indicator of conservation practice outcomes in rangeland systems. Recent technological advances enable assessment at scales appropriate to inform management by providing spatially comprehensive estimates of productivity that are partitioned by plant functional group across all contiguous US rangelands. We partnered with the Sage Grouse and Lesser Prairie-Chicken Initiatives and the Nebraska Natural Legacy Project to demonstrate the ability of these new datasets to quantify multi-scale changes and heterogeneity in plant biomass following mechanical tree removal, prescribed fire, and prescribed grazing. In Oregon's sagebrush steppe, for example, juniper tree removal resulted in a 21% increase in one pasture's productivity and an 18% decline in another. In Nebraska's Loess Canyons, perennial grass productivity initially declined 80% at sites invaded by trees that were prescriptively burned, but then fully recovered post-fire, representing a 492% increase from nadir. In Kansas' Shortgrass Prairie, plant biomass increased 4-fold (966,809 kg/ha) in pastures that were prescriptively grazed, with gains highly dependent upon precipitation as evidenced by sensitivity of remotely sensed estimates (SD ± 951,308 kg/ha). Our results emphasize that next-generation remote sensing datasets empower land managers to move beyond simplistic control versus treatment study designs to explore nuances in plant biomass in unprecedented ways. The products of new remote sensing technologies also accelerate adaptive management and help communicate wildlife and livestock forage benefits from management to diverse stakeholders.

Impact of COVID-19 on emergency department management of stroke and STEMI. A narrative review.

The novel coronavirus of 2019 (COVID-19) has resulted in a global pandemic; COVID-19 has resulted in significant challenges in the delivery of healthcare, including emergency management of multiple diagnoses, such as stroke and ST-segment myocardial infarction (STEMI). The aim of this study was to identify the impacts of the COVID-19 pandemic on emergency department care of stroke and STEMI patients. In this study a review of the available literature was performed using pre-defined search terms, inclusion criteria, and exclusion criteria. Our analysis, using a narrative review format, indicates that there was not a significant change in time required for key interventions for stroke and STEMI emergent management, including imaging (door-to-CT), tPA administration (door-to-needle), angiographic reperfusion (door-to-puncture), and percutaneous coronary intervention (door-to-balloon). Potential future areas of investigation include how emergency department (ED) stroke and STEMI care has adapted in response to different COVID-19 variants and stages of the pandemic, as well as identifying strategies used by EDs that were successful in providing effective emergency care in the face of the pandemic.

Biotic vs abiotic controls on temporal sensitivity of primary production to precipitation across North American drylands.

Dryland net primary productivity (NPP) is sensitive to temporal variation in precipitation (PPT), but the magnitude of this 'temporal sensitivity' varies spatially. Hypotheses for spatial variation in temporal sensitivity have often emphasized abiotic factors, such as moisture limitation, while overlooking biotic factors, such as vegetation structure. We tested these hypotheses using spatiotemporal models fit to remote-sensing data sets to assess how vegetation structure and climate influence temporal sensitivity across five dryland ecoregions of the western USA. Temporal sensitivity was higher in locations and ecoregions dominated by herbaceous vegetation. By contrast, much less spatial variation in temporal sensitivity was explained by mean annual PPT. In fact, ecoregion-specific models showed inconsistent associations of sensitivity and PPT; whereas sensitivity decreased with increasing mean annual PPT in most ecoregions, it increased with mean annual PPT in the most arid ecoregion, the hot deserts. The strong, positive influence of herbaceous vegetation on temporal sensitivity indicates that herbaceous-dominated drylands will be particularly sensitive to future increases in precipitation variability and that dramatic changes in cover type caused by invasions or shrub encroachment will lead to changes in dryland NPP dynamics, perhaps independent of changes in precipitation.

The Emergency Medicine Workforce: Shortage Resolving, Future Surplus Expected.

INTRODUCTION: The emergency medicine (EM) workforce has been growing at a rapid rate, fueled by a large increase in the number of EM residency programs and growth in the number of Advanced Practice Providers (APPs). OBJECTIVES: To review current available data on patient volumes and characteristics, the overall physician workforce, the current emergency physician (EP) workforce, and to project emergency physician staffing needs into the future. METHODS: Data was obtained through review of the current medical literature, reports from certifying organizations and professional societies, Web searches for alternative sources, and published governmental data. RESULTS: We conservatively estimate the demand for emergency clinicians to grow by ∼1.8% per year. The actual demand for EPs will likely be lower, considering the higher growth rates seen by APPs, likely offsetting the need for increasing numbers of EPs. We estimate the overall supply of board-certified or board-eligible EPs to increase by at least 4% in the near-term, which includes losses due to attrition. In light of this, we conservatively estimate the supply of board-certified or eligible EPs should exceed demand by at least 2.2% per year. In the intermediate term, it is possible that the supply of board-certified or eligible EPs could exceed demand by 3% or more per year. Using 2.2% growth, we estimate that the number of board-certified or board-eligible EPs should meet the anticipated demand for EPs as early as the start of 2021. Furthermore, extrapolating current trends, we anticipate the EP workforce could be 20-30% oversupplied by 2030. CONCLUSIONS: Historically, there has been a significant shortage of EPs. We project that this shortage may resolve quickly, and there is the potential for a significant oversupply in the future.

The Mortality of Periviable and Extremely Premature Infants and Their Impact on the Overall Neonatal Mortality Rate.

To investigate mortality in periviable neonates ≤23 weeks gestational age and calculate its impact on overall neonatal mortality rate over a 12-year period (1998-2009). Verify if periviable mortality decreased in the period (2010-2015). Retrospective review. Neonatal mortality rate per 1000 live births was 11.4. Three hundred forty-nine live birth infants weighed ≤500 g and 336 died. Their proportion to the total neonatal mortality rate was 48.6%; out of 298 periviables 146 (43%) were ≤20 weeks gestational age. In 269 (80%) we could not determine the cause of death. Two hundred ninety-seven neonates (88.3%) died in the delivery room. Sixteen (5%) had an autopsy. Neonatal mortality rate from periviability was 96.2% and constituted half of the overall rate in the period (1998-2009). There was not significant reduction of periviable mortality between 2010 and 2015. Current live birth definition and a reporting system that considers a 100 g periviable live birth infant as a neonatal death has placed Ohio and the United States at a significant disadvantage compared to other countries using different reporting systems.

Human land uses reduce climate connectivity across North America.

Climate connectivity, the ability of a landscape to promote or hinder the movement of organisms in response to a changing climate, is contingent on multiple factors including the distance organisms need to move to track suitable climate over time (i.e. climate velocity) and the resistance they experience along such routes. An additional consideration which has received less attention is that human land uses increase resistance to movement or alter movement routes and thus influence climate connectivity. Here we evaluate the influence of human land uses on climate connectivity across North America by comparing two climate connectivity scenarios, one considering climate change in isolation and the other considering climate change and human land uses. In doing so, we introduce a novel metric of climate connectivity, 'human exposure', that quantifies the cumulative exposure to human activities that organisms may encounter as they shift their ranges in response to climate change. We also delineate potential movement routes and evaluate whether the protected area network supports movement corridors better than non-protected lands. We found that when incorporating human land uses, climate connectivity decreased; climate velocity increased on average by 0.3 km/year and cumulative climatic resistance increased for ~83% of the continent. Moreover, ~96% of movement routes in North America must contend with human land uses to some degree. In the scenario that evaluated climate change in isolation, we found that protected areas do not support climate corridors at a higher rate than non-protected lands across North America. However, variability is evident, as many ecoregions contain protected areas that exhibit both more and less representation of climate corridors compared to non-protected lands. Overall, our study indicates that previous evaluations of climate connectivity underestimate climate change exposure because they do not account for human impacts.

Coproducing Science to Inform Working Lands: The Next Frontier in Nature Conservation.

Conservationists are increasingly convinced that coproduction of science enhances its utility in policy, decision-making, and practice. Concomitant is a renewed reliance on privately owned working lands to sustain nature and people. We propose a coupling of these emerging trends as a better recipe for conservation. To illustrate this, we present five elements of coproduction, contrast how they differ from traditional approaches, and describe the role of scientists in successful partnerships. Readers will find coproduction more demanding than the loading dock approach to science delivery but will also find greater rewards, relevance, and impact. Because coproduction is novel and examples of it are rare, we draw on our roles as scientists within the US Department of Agriculture-led Sage Grouse Initiative, North America's largest effort to conserve the sagebrush ecosystem. As coproduction and working lands evolve, traditional approaches will be replaced in order to more holistically meet the needs of nature and people.

Tree-ring isotopes capture interannual vegetation productivity dynamics at the biome scale.

Historical and future trends in net primary productivity (NPP) and its sensitivity to global change are largely unknown because of the lack of long-term, high-resolution data. Here we test whether annually resolved tree-ring stable carbon (δ13C) and oxygen (δ18O) isotopes can be used as proxies for reconstructing past NPP. Stable isotope chronologies from four sites within three distinct hydroclimatic environments in the eastern United States (US) were compared in time and space against satellite-derived NPP products, including the long-term Global Inventory Modeling and Mapping Studies (GIMMS3g) NPP (1982-2011), the newest high-resolution Landsat NPP (1986-2015), and the Moderate Resolution Imaging Spectroradiometer (MODIS, 2001-2015) NPP. We show that tree-ring isotopes, in particular δ18O, correlate strongly with satellite NPP estimates at both local and large geographical scales in the eastern US. These findings represent an important breakthrough for estimating interannual variability and long-term changes in terrestrial productivity at the biome scale.

Patterns of rangeland productivity and land ownership: Implications for conservation and management.

Rangelands cover 40-50% of the Earth's terrestrial surface. While often characterized by limited, yet variable resource availability, rangelands are vital for humans, providing numerous ecosystem goods and services. In the conterminous United States (CONUS), the dominant component of rangeland conservation is a network of public rangelands, concentrated in the west. Public rangelands are interspersed with private and tribal rangelands resulting in a complex mosaic of land tenure and management priorities. We quantify ownership patterns of rangeland production at multiple scales across CONUS and find that both total production and average productivity of private rangelands is more than twice that of public and tribal rangelands. At finer scales, private rangelands are consistently more productive than their public counterparts. We also demonstrate an inverse relationship between public rangeland acreage and productivity. While conserving acreage is crucial to rangeland conservation, just as critical are broad-scale ecological patterns and processes that sustain ecosystem services. Across CONUS, ownership regimes capture distinct elements of these patterns and services, demonstrated through disparate production dynamics. As ownership determines the range of feasible conservation actions, and the technical and financial resources available to implement them, understanding ownership-production dynamics is critical for effective and sustained conservation of rangeland ecosystem services.

Phenology largely explains taller grass at successful nests in greater sage-grouse.

Much interest lies in the identification of manageable habitat variables that affect key vital rates for species of concern. For ground-nesting birds, vegetation surrounding the nest may play an important role in mediating nest success by providing concealment from predators. Height of grasses surrounding the nest is thought to be a driver of nest survival in greater sage-grouse (Centrocercus urophasianus; sage-grouse), a species that has experienced widespread population declines throughout their range. However, a growing body of the literature has found that widely used field methods can produce misleading inference on the relationship between grass height and nest success. Specifically, it has been demonstrated that measuring concealment following nest fate (failure or hatch) introduces a temporal bias whereby successful nests are measured later in the season, on average, than failed nests. This sampling bias can produce inference suggesting a positive effect of grass height on nest survival, though the relationship arises due to the confounding effect of plant phenology, not an effect on predation risk. To test the generality of this finding for sage-grouse, we reanalyzed existing datasets comprising >800 sage-grouse nests from three independent studies across the range where there was a positive relationship found between grass height and nest survival, including two using methods now known to be biased. Correcting for phenology produced equivocal relationships between grass height and sage-grouse nest survival. Viewed in total, evidence for a ubiquitous biological effect of grass height on sage-grouse nest success across time and space is lacking. In light of these findings, a reevaluation of land management guidelines emphasizing specific grass height targets to promote nest success may be merited.

Seasonal drought in North America's sagebrush biome structures dynamic mesic resources for sage-grouse.

The North American semi-arid sagebrush, Artemisia spp., biome exhibits considerable climatic complexity driving dynamic spatiotemporal shifts in primary productivity. Greater and Gunnison sage-grouse, Centrocercus urophasianus and C. minimus, are adapted to patterns of resource intermittence and rely on stable adult survival supplemented by occasional recruitment pulses when climatic conditions are favorable. Predictions of intensifying water scarcity raise concerns over new demographic bottlenecks impacting sage-grouse populations in drought-sensitive landscapes. We estimate biome-wide mesic resource productivity from 1984 to 2016 using remote sensing to identify patterns of food availability influencing selective pressures on sage-grouse. We linked productivity to abiotic factors to examine effects of seasonal drought across time, space, and land tenure, with findings partitioned along gradients of ecosystem water balance within Great Basin, Rocky Mountains and Great Plains regions. Precipitation was the driver of mesic resource abundance explaining ≥70% of variance in drought-limited vegetative productivity. Spatiotemporal shifts in mesic abundance were apparent given biome-wide climatic trends that reduced precipitation below three-quarters of normal in 20% of years. Drought sensitivity structured grouse populations wherein landscapes with the greatest uncertainty in mesic abundance and distribution supported the fewest grouse. Privately owned lands encompassed 40% of sage-grouse range, but contained a disproportional 68% of mesic resources. Regional drought sensitivity identified herein acted as ecological minimums to influence differences in landscape carrying capacity across sage-grouse range. Our model depictions likely reflect a new normal in water scarcity that could compound impacts of demographic bottlenecks in Great Basin and Great Plains. We conclude that long-term population maintenance depends on a diversity of drought resistant mesic resources that offset climate driven variability in vegetative productivity. We recommend a holistic public-private lands approach to mesic restoration to offset a deepening risk of water scarcity.

A phase I trial of paclitaxel, cisplatin, and veliparib in the treatment of persistent or recurrent carcinoma of the cervix: an NRG Oncology Study (NCT#01281852).

Background: Preclinical studies demonstrate poly(ADP-ribose) polymerase (PARP) inhibition augments apoptotic response and sensitizes cervical cancer cells to the effects of cisplatin. Given the use of cisplatin and paclitaxel as first-line treatment for persistent or recurrent cervical cancer, we aimed to estimate the maximum tolerated dose (MTD) of the PARP inhibitor veliparib when added to chemotherapy. Patients and methods: Women with persistent or recurrent cervical carcinoma not amenable to curative therapy were enrolled. Patients had to have received concurrent chemotherapy and radiation as well as possible consolidation chemotherapy; have adequate organ function. The trial utilized a standard 3 + 3 phase I dose escalation with patients receiving paclitaxel 175 mg/m2 on day 1, cisplatin 50 mg/m2 on day 2, and escalating doses of veliparib ranging from 50 to 400 mg orally two times daily on days 1-7. Cycles occurred every 21 days until progression. Dose-limiting toxicities (DLTs) were assessed at first cycle. Fanconi anemia complementation group D2 (FANCD2) foci was evaluated in tissue specimens as a biomarker of response. Results: Thirty-four patients received treatment. DLTs (n = 1) were a grade 4 dyspnea, a grade 3 neutropenia lasting ≥3 weeks, and febrile neutropenia. At 400 mg dose level (DL), one of the six patients had a DLT, so the MTD was not reached. Across DLs, the objective response rate (RR) for 29 patients with measurable disease was 34% [95% confidence interval (CI), 20%-53%]; at 400 mg DL, the RR was 60% (n = 3/5; 95% CI, 23%-88%). Median progression-free survival was 6.2 months (95% CI, 2.9-10.1), and overall survival was 14.5 months (95% CI, 8.2-19.4). FANCD2 foci was negative or heterogeneous in 31% of patients and present in 69%. Objective RR were not associated with FANCD2 foci (P = 0.53). Conclusions: Combining veliparib with paclitaxel and cisplatin as first-line treatment for persistent or recurrent cervical cancer patients is safe and feasible. Clinical trial information: NCT01281852.