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Abstract Drought-induced productivity reductions and tree mortality have been increasing in recent decades in forests around the globe. Developing adaptation strategies hinges on an adequate understanding of the mechanisms governing the drought vulnerability of forest stands. Prescribed reduction in stand density has been used as a management tool to reduce water stress and wildfire risk, but the processes that modulate fine-scale variations in plant water supply and water demand are largely missing in ecosystem models. We used an ecohydrological model that couples plant hydraulics with groundwater hydrology to examine how within-stand variations in tree spatial arrangements and topography might mitigate forest vulnerability to drought at individual-tree and stand scales. Our results demonstrated thinning generally ameliorated plant hydraulic stress and improved carbon and water fluxes of the remaining trees, although the effectiveness varied by climate and topography. Variable thinning that adjusted thinning intensity based on topography-mediated water availability achieved higher stand productivity and lower mortality risk, compared to evenly-spaced thinning at comparable intensities. The results from numerical experiments provided mechanistic evidence that topography mediates the effectiveness of thinning and highlighted the need for an explicit consideration of within-stand heterogeneity in trees and abiotic environments when designing forest thinning to mitigate drought impacts. 

Abstract Arynes are highly reactive and versatile intermediates for the functionalization of aromatic rings that are often generated using strong bases or fluoride sources, which, in some cases, can limit functional group tolerance. Here we demonstrate that triaryloxonium ions can be transformed into arynes through treatment with solid potassium phosphate at room temperature. A substantial range of functional group-bearing arynes, including 4,5-pyrimidynes, may be generated and trapped using cycloaddition reactions with high yields. Other arynophiles including nitrones, alkenes and azides are compatible with these conditions. Quantum computation in conjunction with an intramolecular kinetic isotope study is consistent with an elimination, unimolecular, conjugate base-like mechanism of elimination to form the aryne. These investigations demonstrate that the oxonium ion is a powerful electron-withdrawing group and a particularly effective leaving group. We anticipate that this study will stimulate further investigations into the synthetic utility of aryl oxonium ions. 

Scientists seek to understand the causal processes that generate sustainability problems and determine effective solutions. Yet, causal inquiry in nature–society systems is hampered by conceptual and methodological challenges that arise from nature–society interdependencies and the complex dynamics they create. Here, we demonstrate how sustainability scientists can address these challenges and make more robust causal claims through better integration between empirical analyses and process- or agent-based modeling. To illustrate how these different epistemological traditions can be integrated, we present four studies of air pollution regulation, natural resource management, and the spread of COVID-19. The studies show how integration can improve empirical estimates of causal effects, inform future research designs and data collection, enhance understanding of the complex dynamics that underlie observed temporal patterns, and elucidate causal mechanisms and the contexts in which they operate. These advances in causal understanding can help sustainability scientists develop better theories of phenomena where social and ecological processes are dynamically intertwined and prior causal knowledge and data are limited. The improved causal understanding also enhances governance by helping scientists and practitioners choose among potential interventions, decide when and how the timing of an intervention matters, and anticipate unexpected outcomes. Methodological integration, however, requires skills and efforts of all involved to learn how members of the respective other tradition think and analyze nature–society systems. 

Abstract Optogenetics has transformed studies of neural circuit function, but remains challenging to apply to non-human primates (NHPs). A major challenge is delivering intense, spatiotemporally-precise, patterned photostimulation across large volumes in deep tissue. Such stimulation is critical, for example, to modulate selectively deep-layer corticocortical feedback circuits. To address this need, we have developed the Utah Optrode Array (UOA), a 10×10 glass needle waveguide array fabricated atop a novel opaque optical interposer, and bonded to an electrically addressable µLED array. In vivo experiments with the UOA demonstrated large-scale, spatiotemporally precise, activation of deep circuits in NHP cortex. Specifically, the UOA permitted both focal (confined to single layers/columns), and widespread (multiple layers/columns) optogenetic activation of deep layer neurons, as assessed with multi-channel laminar electrode arrays, simply by varying the number of activated µLEDs and/or the irradiance. Thus, the UOA represents a powerful optoelectronic device for targeted manipulation of deep-layer circuits in NHP models. 

How barriers to gene flow arise and are maintained are key questions in evolutionary biology. Speciation research has mainly focussed on barriers that occur either before mating or after zygote formation. In comparison, postmating prezygotic (PMPZ) isolation – a barrier that acts after gamete release but before zygote formation – is less frequently investigated but may hold a unique role in generating biodiversity. Here we discuss the distinctive features of PMPZ isolation, including the primary drivers and molecular mechanisms underpinning PMPZ isolation. We then present the first comprehensive survey of PMPZ isolation research, revealing that it is a widespread form of prezygotic isolation across eukaryotes. The survey also exposes obstacles in studying PMPZ isolation, in part attributable to the challenges involved in directly measuring PMPZ isolation and uncovering its causal mechanisms. Finally, we identify outstanding knowledge gaps and provide recommendations for improving future research on PMPZ isolation. This will allow us to better understand the nature of this often-neglected reproductive barrier and its contribution to speciation. 

The article argues that mainstream value-sensitive approaches to design have been based on narrow understandings of personhood and social dynamics, which are biased toward Western Educated Industrialized Rich and Democratic cultures and contradicted by empirical evidence. To respond to this weakness, the article suggests that design may benefit from focusing on user behaviours from the joint perspective of values and norms, especially across cultural contexts. As such, it proposes Norm Sensitive Design as a complement to value-sensitive approaches when designing and implementing new technologies. Versus values, norms serve as more accurate predictors or descriptors of behaviours and can thus support valuesensitive approaches to realize the aspiration of informing user behaviour via design. The article makes two key contributions. On the theoretical side, it promotes the consideration of norms in design. On the practical side, it offers designers and instructors prompts for reflecting on design ethics from the perspective of norms. 

Abstract The control of tetrahedral carbon stereocentres remains a focus of modern synthetic chemistry and is enabled by their configurational stability. By contrast, trisubstituted nitrogen 1 , phosphorus 2 and sulfur compounds 3 undergo pyramidal inversion, a fundamental and well-recognized stereochemical phenomenon that is widely exploited 4 . However, the stereochemistry of oxonium ions—compounds bearing three substituents on a positively charged oxygen atom—is poorly developed and there are few applications of oxonium ions in synthesis beyond their existence as reactive intermediates 5,6 . There are no examples of configurationally stable oxonium ions in which the oxygen atom is the sole stereogenic centre, probably owing to the low barrier to oxygen pyramidal inversion 7 and the perception that all oxonium ions are highly reactive. Here we describe the design, synthesis and characterization of a helically chiral triaryloxonium ion in which inversion of the oxygen lone pair is prevented through geometric restriction to enable it to function as a determinant of configuration. A combined synthesis and quantum calculation approach delineates design principles that enable configurationally stable and room-temperature isolable salts to be generated. We show that the barrier to inversion is greater than 110 kJ mol −1 and outline processes for resolution. This constitutes, to our knowledge, the only example of a chiral non-racemic and configurationally stable molecule in which the oxygen atom is the sole stereogenic centre. 

Abstract Per‐ and polyfluoroalkyl substances (PFAS) and mercury (Hg) are harmful compounds that are widely present in the environment, partly due to spills and atmospheric pollution. The presence of PFAS and Hg in the tissues of animals that are harvested by rural and Indigenous Alaskans is of great concern, yet fish in Arctic Alaska have not previously been assessed for concentrations of PFAS. Fish species of subsistence and recreational importance were collected from nearshore Beaufort and Chukchi Sea, Alaska habitats and assessed for PFAS and total mercury concentrations [THg]. We found multiple PFAS compounds present at low levels (<3 μg/kg) in the muscle tissue of inconnu, broad whitefish, Dolly Varden char, Arctic flounder, saffron cod, humpback whitefish, and least cisco. In addition, [THg] levels in these fish were well below levels triggering local fish consumption guidelines (<170 μg/kg). These initial results indicate no evidence of the Alaska Arctic nearshore fish species examined as an avenue of PFAS or Hg exposure to people who harvest them. However, sources and trends of these contaminants in the Arctic require further investigation. Environ Toxicol Chem 2023;00:1–7. © 2023 SETAC