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Abstract Hydrophosphination using calcium compounds as catalysts under irradiation is described as a foray into s‐block photocatalysis. Transition‐metal compounds have been highly successful hydrophosphination catalysts under photochemical conditions, utilizing substrates previously considered inaccessible. A calcium hydrophosphination precatalyst, Ca(nacnac) (THF) (N(SiMe3)2) (1, nacnac = HC[(C(Me)N‐2,6‐iPr2C6H3)]2), reported by Barrett and Hill, as well as the presumed intermediate, Ca(nacnac) (THF) (PPh2) (2), and the Schlenk equilibrium product, Ca[N(SiMe3)2]2(THF)2(3) were screened under photochemical conditions with a range of unsaturated substrates including styrenic alkenes, Michael acceptors, and dienes with modest to excellent conversions, though unactivated alkenes were inaccessible. All compounds exhibit enhanced catalysis under irradiation by light emitting diode (LED)‐generated blue light. Nacnac‐supported compounds generate radicals as evidenced by Electron Paramagnetic Resonance (EPR) spectroscopy and radical trapping reactions, whereas unsupported calcium compounds are EPR silent and appear to undergo hydrophosphination akin to thermal reactions with these compounds. These results buttress the notion that photoactivation of π‐basic ligands is a broad phenomenon, extending beyond the d‐block, but like d‐block metals, consideration of ancillary ligands is essential to avoid radical reactivity.more » « less
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Free, publicly-accessible full text available March 19, 2026
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Summary Grasses are fundamental to human survival, providing a large percentage of our calories, fuel, and fodder for livestock, and an enormous global carbon sink. A particularly important part of the grass plant is the grain‐producing inflorescence that develops in response to both internal and external signals that converge at the shoot tip to influence meristem behavior. Abiotic signals that trigger reproductive development vary across the grass family, mostly due to the unique ecological and phylogenetic histories of each clade. The time it takes a grass to flower has implications for its ability to escape harsh environments, while also indirectly affecting abiotic stress tolerance, inflorescence architecture, and grain yield. Here, we synthesize recent insights into the evolution of grass flowering time in response to past climate change, particularly focusing on genetic convergence in underlying traits. We then discuss how and why the rewiring of a shared ancestral flowering pathway affects grass yields, and outline ways in which researchers are using this and other information to breed higher yielding, climate‐proof cereal crops.more » « less
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Abstract Pressure is mounting to minimize the carbon footprint of chemical industry while increasing its sustainability. An argument is made that working from Green Chemistry principles during discovery‐based catalysis results in effective chemistry and circumvents a need to “rediscover” chemical reactivity under sustainable conditions. Examples of comparative success in selected examples of hydrophosphination catalysis in various degrees of development are provided to support two main ideas: 1) Starting from more sustainable practices in chemical discovery is inertia in methodology that should be overcome, and 2) substantial challenges remain in catalysis for which sustainable solutions would positively impact other areas of chemistry. Examples of successes, even in the face of the challenges noted, are presented herein as indications that even as a starting point, sustainability can meet short‐ and long‐term needs. These ideas indicate critical but simple strategies for fundamental research to be impactful in the sustainability of the chemical industry broadly.more » « less
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In organisms with complex life cycles, life stages that are most susceptible to environmental stress may determine species persistence in the face of climate change. Early embryos ofDrosophila melanogasterare particularly sensitive to acute heat stress, yet tropical embryos have higher heat tolerance than temperate embryos, suggesting adaptive variation in embryonic heat tolerance. We compared transcriptomic responses to heat stress among tropical and temperate embryos to elucidate the gene regulatory basis of divergence in embryonic heat tolerance. The transcriptomes of tropical and temperate embryos differed in both constitutive and heat-stress-induced responses of the expression of relatively few genes, including genes involved in oxidative stress. Most of the transcriptomic response to heat stress was shared among all embryos. Embryos shifted the expression of thousands of genes, including increases in the expression of heat shock genes, suggesting robust zygotic gene activation and demonstrating that, contrary to previous reports, early embryos are not transcriptionally silent. The involvement of oxidative stress genes corroborates recent reports on the critical role of redox homeostasis in coordinating developmental transitions. By characterizing adaptive variation in the transcriptomic basis of embryonic heat tolerance, this study is a novel contribution to the literature on developmental physiology and developmental genetics.more » « less
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Crop switching, in which farmers grow a crop that is novel to a given field, can help agricultural systems adapt to changing environmental, cultural, and market forces. Yet while regional crop production trends receive significant attention, relatively little is known about the local-scale crop switching that underlies these macrotrends. We characterized local crop-switching patterns across the United States using the US Department of Agriculture (USDA) Cropland Data Layer, an annual time series of high resolution (30 m pixel size) remote-sensed cropland data from 2008 to 2022. We found that at multiple spatial scales, crop switching was most common in sparsely cultivated landscapes and in landscapes with high crop diversity, whereas it was low in homogeneous, highly agricultural areas such as the Midwestern corn belt, suggesting a number of potential social and economic mechanisms influencing farmers’ crop choices. Crop-switching rates were high overall, occurring on more than 6% of all US cropland in the average year. Applying a framework that classified crop switches based on their temporal novelty (crop introduction versus discontinuation), spatial novelty (locally divergent versus convergent switching), and categorical novelty (transformative versus incremental switching), we found distinct spatial patterns for these three novelty dimensions, indicating a dynamic and multifaceted set of cropping changes across US farms. Collectively, these results suggest that innovation through crop switching is playing out very differently in various parts of the country, with potentially significant implications for the resilience of agricultural systems to changes in climate and other systemic trends.more » « less
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Epidemic models study the spread of undesired agents through populations, be it infectious diseases through a country, misinformation in social media or pests infesting a region. In combating these epidemics, we rely neither on global top-down interventions, nor solely on individual adaptations. Instead, interventions commonly come from local institutions such as public health departments, moderation teams on social media platforms or other forms of group governance. Classic models, which are often individual or agent-based, are ill-suited to capture local adaptations. We leverage developments of institutional dynamics based on cultural group selection to study how groups attempt local control of an epidemic by taking inspiration from the successes and failures of other groups. Incorporating institutional changes into epidemic dynamics reveals paradoxes: a higher transmission rate can result in smaller outbreaks as does decreasing the speed of institutional adaptation. When groups perceive a contagion as more worrisome, they can invest in improved policies and, if they maintain these policies long enough to have impact, lead to a reduction in endemicity. By looking at the interplay between the speed of institutions and the transmission rate of the contagions, we find rich coevolutionary dynamics that reflect the complexity of known biological and social contagions.more » « less
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Summary Plastic responses of plants to their environment vary as a result of genetic differentiation within and among species. To accurately predict rangewide responses to climate change, it is necessary to characterize genotype‐specific reaction norms across the continuum of historic and future climate conditions comprising a species' range.The North American hybrid zone ofPopulus trichocarpaandPopulus balsamiferarepresents a natural system that has been shaped by climate, geography, and introgression. We leverage a dataset containing 44 clonal genotypes from this natural hybrid zone, planted across 17 replicated common garden experiments spanning a broad climatic range. Growth and mortality were measured over 2 yr, enabling us to model reaction norms for each genotype across these tested environments.Species ancestry and intraspecific genomic variation significantly influenced growth across environments, with genotypic variation in reaction norms reflecting a trade‐off between cold tolerance and growth. Using modeled reaction norms for each genotype, we predicted that genotypes with moreP. trichocarpaancestry may gain an advantage under warmer climates.Spatial shifts of the hybrid zone could facilitate the spread of beneficial alleles into novel climates. These results highlight that genotypic variation in responses to temperature will have landscape‐level effects.more » « less
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