Continuous Enantioselective α-Alkylation of Ketones via Direct Photoexcitation.

Motivated by the scarcity of enantioselective direct intermolecular α-alkylation reactions of ketones with simple alkyl halides, we report a photo-organocatalytic process to access diethyl 2-(2-oxocyclohexyl)malonate and derivatives in good yield and enantioselectivity. The reaction design is based on highly abundant and nature-derived 9-amino-9-deoxy-epi-cinchona alkaloids to activate ketones as transient secondary enamines, which exist unfavorably in equilibrium with imines. These condensed species can serve as powerful photoinitiators via direct photoexcitation. This concept provides access to both enantiomeric antipodes. In addition to introducing an uncomplicated batch-optimized procedure, we investigated the feasibility and limitations of implementing the reaction in continuous flow, thus enabling to obtain diethyl 2-(2-oxocyclohexyl)malonate with a productivity of 47 µmol/h and 84% enantioselectivity.

Warm and arid regions of the world are hotspots of superorganism complexity.

Biologists have long been fascinated by the processes that give rise to phenotypic complexity of organisms, yet whether there exist geographical hotspots of phenotypic complexity remains poorly explored. Phenotypic complexity can be readily observed in ant colonies, which are superorganisms with morphologically differentiated queen and worker castes analogous to the germline and soma of multicellular organisms. Several ant species have evolved 'worker polymorphism', where workers in a single colony show quantifiable differences in size and head-to-body scaling. Here, we use 256 754 occurrence points from 8990 ant species to investigate the geography of worker polymorphism. We show that arid regions of the world are the hotspots of superorganism complexity. Tropical savannahs and deserts, which are typically species-poor relative to tropical or even temperate forests, harbour the highest densities of polymorphic ants. We discuss the possible adaptive advantages that worker polymorphism provides in arid environments. Our work may provide a window into the environmental conditions that promote the emergence of highly complex phenotypes.

Sodium co-limits and catalyzes macronutrients in a prairie food web.

Nitrogen and phosphorus frequently limit terrestrial plant production, but have a mixed record in regulating the abundance of terrestrial invertebrates. We contrasted four ways that Na could interact with an NP fertilizer to shape the plants and invertebrates of an inland prairie. We applied NP and Na to m2 plots in a factorial design. Aboveground invertebrate abundance was independently co-limited by NaCl and NP, but with +NP plots supporting more individuals. We suggest the disparity arises because NP enhanced plant height by 35% (1 SD) over controls, providing both food and habitat, whereas NaCl provides only food. Belowground invertebrates showed evidence of serial co-limitation, where NaCl additions alone were ineffectual, but catalyzed access to NP. This suggests the increased belowground food availability in NP plots increased Na demand. Na and NP supply rates vary with climate, land use, and with inputs like urine. The co-limitation and catalysis of N and P by Na thus has the potential for predicting patterns of abundance and diversity across spatial scales.

Biogeochemistry drives diversity in the prokaryotes, fungi, and invertebrates of a Panama forest.

Humans are both fertilizing the world and depleting its soils, decreasing the diversity of aquatic ecosystems and terrestrial plants in the process. We know less about how nutrients shape the abundance and diversity of the prokaryotes, fungi, and invertebrates of Earth's soils. Here we explore this question in the soils of a Panama forest subject to a 13-yr fertilization with factorial combinations of nitrogen (N), phosphorus (P), and potassium (K) and a separate micronutrient cocktail. We contrast three hypotheses linking biogeochemistry to abundance and diversity. Consistent with the Stress Hypothesis, adding N suppressed the abundance of invertebrates and the richness of all three groups of organisms by ca. 1 SD or more below controls. Nitrogen addition plots were 0.8 pH units more acidic with 18% more exchangeable aluminum, which is toxic to both prokaryotes and eukaryotes. These stress effects were frequently reversed, however, when N was added with P (for prokaryotes and invertebrates) and with added K (for fungi). Consistent with the Abundance Hypothesis, adding P generally increased prokaryote and invertebrate diversity, and adding K enhanced invertebrate diversity. Also consistent with the Abundance Hypothesis, increases in invertebrate abundance generated increases in richness. We found little evidence for the Competition Hypothesis: that single nutrients suppressed diversity by favoring a subset of high nutrient specialists, and that nutrient combinations suppressed diversity even more. Instead, combinations of nutrients, and especially the cation/micronutrient treatment, yielded the largest increases in richness in the two eukaryote groups. In sum, changes in soil biogeochemistry revealed a diversity of responses among the three dominant soil groups, positive synergies among nutrients, and-in contrast with terrestrial plants-the frequent enhancement of soil biodiversity.

Dietary Isoflavone-Dependent and Estradiol Replacement Effects on Body Weight in the Ovariectomized (OVX) Rat.

17ß-Estradiol is known to regulate energy metabolism and body weight. Ovariectomy results in body weight gain while estradiol administration results in a reversal of weight gain. Isoflavones, found in rodent chow, can mimic estrogenic effects making it crucial to understand the role of these compounds on metabolic regulation. The goal of this study is to examine the effect of dietary isoflavones on body weight regulation in the ovariectomized rat. This study will examine how dietary isoflavones can interact with estradiol treatment to affect body weight. Consistent with previous findings, animals fed an isoflavone-rich diet had decreased body weight (p<0.05), abdominal fat (p<0.05), and serum leptin levels (p<0.05) compared to animals fed an isoflavone-free diet. Estradiol replacement resulted in decreased body weight (p<0.05), abdominal fat (p<0.05), and serum leptin (p<0.05). Current literature suggests the involvement of cytokines in the inflammatory response of body weight gain. We screened a host of cytokines and chemokines that may be altered by dietary isoflavones or estradiol replacement. Serum cytokine analysis revealed significant (p<0.05) diet-dependent increases in inflammatory cytokines (keratinocyte-derived chemokine). The isoflavone-free diet in OVX rats resulted in the regulation of the following cytokines and chemokines: interleukin-10, interleukin-18, serum regulated on activation, normal T cell expressed and secreted, and monocyte chemoattractant protein-1 (p<0.05). Overall, these results reveal that estradiol treatment can have differential effects on energy metabolism and body weight regulation depending on the presence of isoflavones in rodent chow.

The latitudinal species richness gradient in New World woody angiosperms is consistent with the tropical conservatism hypothesis.

Plant diversity, like that of most other taxonomic groups, peaks in the tropics, where climatic conditions are warm and wet, and it declines toward the temperate and polar zones as conditions become colder and drier, with more seasonally variable temperatures. Climate and evolutionary history are often considered competing explanations for the latitudinal gradient, but they are linked by the evolutionarily conserved environmental adaptations of species and the history of Earth's climate system. The tropical conservatism hypothesis (TCH) invokes niche conservatism, climatic limitations on establishment and survival, and paleoclimatic history to explain the latitudinal diversity gradient. Here, we use latitudinal distributions for over 12,500 woody angiosperm species, a fossil-calibrated supertree, and null modeling to test predictions of the TCH. Regional assemblages in the northern and southern temperate zones are less phylogenetically diverse than expected based on their species richness, because temperate taxa are clustered into relatively few clades. Moreover, lineages with temperate affinities are generally younger and nested within older, more tropical lineages. As predicted by the TCH, the vast majority of temperate lineages have arisen since global cooling began at the Eocene-Oligocene boundary (34 Mya). By linking physiological tolerances of species to evolutionary and biogeographic processes, phylogenetic niche conservatism may provide a theoretical framework for a generalized explanation for Earth's predominant pattern of biodiversity.

Constancy in Functional Space across a Species Richness Anomaly.

The relationship between large-scale gradients in species richness and functional diversity provides important information regarding the mechanisms driving patterns of biodiversity. A classic hypothesis in ecology is that strong interspecific interactions should result in an increase in the functional volume of assemblages as the species richness increases, whereas climatic constraints may result in no change in functional volume. Most research of this kind examines latitudinal gradients in species richness, but the results are likely confounded by underlying gradients in climate and phylogenetic composition. We take an alternative approach that examines functional richness across a tree species richness anomaly where species richness doubles from Europe to eastern North America. The results demonstrate that the functional richness on both continents saturates at a similar point as species richness increases and that the packing of functional space becomes tighter. Further, the species richness anomaly is driven primarily by genera unique to North America, but those genera contribute less than expected functional richness to the region, indicating a high level of redundancy with genera shared between the continents. Taken together, the results indicate that the species richness anomaly is associated with diversification within a climatically constrained trait space. More generally, the work demonstrates the power of utilizing species richness anomalies in biodiversity research, particularly when they are coupled with information regarding organismal function.

Biogeographic patterns of soil diazotrophic communities across six forests in North America.

Soil diazotrophs play important roles in ecosystem functioning by converting atmospheric N2 into biologically available ammonium. However, the diversity and distribution of soil diazotrophic communities in different forests and whether they follow biogeographic patterns similar to macroorganisms still remain unclear. By sequencing nifH gene amplicons, we surveyed the diversity, structure and biogeographic patterns of soil diazotrophic communities across six North American forests (126 nested samples). Our results showed that each forest harboured markedly different soil diazotrophic communities and that these communities followed traditional biogeographic patterns similar to plant and animal communities, including the taxa-area relationship (TAR) and latitudinal diversity gradient. Significantly higher community diversity and lower microbial spatial turnover rates (i.e. z-values) were found for rainforests (~0.06) than temperate forests (~0.1). The gradient pattern of TARs and community diversity was strongly correlated (r(2)  > 0.5) with latitude, annual mean temperature, plant species richness and precipitation, and weakly correlated (r(2)  < 0.25) with pH and soil moisture. This study suggests that even microbial subcommunities (e.g. soil diazotrophs) follow general biogeographic patterns (e.g. TAR, latitudinal diversity gradient), and indicates that the metabolic theory of ecology and habitat heterogeneity may be the major underlying ecological mechanisms shaping the biogeographic patterns of soil diazotrophic communities.

Dietary DHA during development affects depression-like behaviors and biomarkers that emerge after puberty in adolescent rats.

DHA is an important omega-3 PUFA that confers neurodevelopmental benefits. Sufficient omega-3 PUFA intake has been associated with improved mood-associated measures in adult humans and rodents, but it is unknown whether DHA specifically influences these benefits. Furthermore, the extent to which development and puberty interact with the maternal diet and the offspring diet to affect mood-related behaviors in adolescence is poorly understood. We sought to address these questions by 1) feeding pregnant rats with diets sufficient or deficient in DHA during gestation and lactation; 2) weaning their male offspring to diets that were sufficient or deficient in DHA; and 3) assessing depression-related behaviors (forced swim test), plasma biomarkers [brain-derived neurotrophic factor (BDNF), serotonin, and melatonin], and brain biomarkers (BDNF) in the offspring before and after puberty. No dietary effects were detected when the offspring were evaluated before puberty. In contrast, after puberty depressive-like behavior and its associated biomarkers were worse in DHA-deficient offspring compared with animals with sufficient levels of DHA. The findings reported here suggest that maintaining sufficient DHA levels throughout development (both pre- and postweaning) may increase resiliency to emotional stressors and decrease susceptibility to mood disorders that commonly arise during adolescence.

Gonadal steroid hormones and the hypothalamo-pituitary-adrenal axis.

The hypothalamo-pituitary-adrenal (HPA) axis represents a complex neuroendocrine feedback loop controlling the secretion of adrenal glucocorticoid hormones. Central to its function is the paraventricular nucleus of the hypothalamus (PVN) where neurons expressing corticotropin releasing factor reside. These HPA motor neurons are a primary site of integration leading to graded endocrine responses to physical and psychological stressors. An important regulatory factor that must be considered, prior to generating an appropriate response is the animal's reproductive status. Thus, PVN neurons express androgen and estrogen receptors and receive input from sites that also express these receptors. Consequently, changes in reproduction and gonadal steroid levels modulate the stress response and this underlies sex differences in HPA axis function. This review examines the make up of the HPA axis and hypothalamo-pituitary-gonadal (HPG) axis and the interactions between the two that should be considered when exploring normal and pathological responses to environmental stressors.

Global phylogenetic structure of the hyperdiverse ant genus Pheidole reveals the repeated evolution of macroecological patterns.

Adaptive radiations are of particular interest owing to what they reveal about the ecological and evolutionary regulation of biodiversity. This applies to localized island radiations such as Darwin's finches, and also to rapid radiations occurring on a global scale. Here we analyse the macroevolution and macroecology of Pheidole, a famously hyperdiverse and ecologically dominant ant genus. We generate and analyse four novel datasets: (i) a robust global phylogeny including 285 Pheidole species, (ii) a global database on regional Pheidole richness in 365 political areas summarizing over 97 000 individual records from more than 6500 studies, (iii) a global database of Pheidole richness from 3796 local communities and (iv) a database of Pheidole body sizes across species. Analysis of the potential climate drivers of richness revealed that the patterns are statistically very similar across different biogeographic regions, with both regional and local richness associated with the same coefficients of temperature and precipitation. This similarity occurs even though phylogenetic analysis shows that Pheidole reached dominance in communities through serial localized radiations into different biomes within different continents and islands. Pheidole body size distributions have likewise converged across geographical regions. We propose these cases of convergence indicate that the global radiation of Pheidole is structured by deterministic factors regulating diversification and diversity.

Global models of ant diversity suggest regions where new discoveries are most likely are under disproportionate deforestation threat.

Most of the described and probably undescribed species on Earth are insects. Global models of species diversity rarely focus on insects and none attempt to address unknown, undescribed diversity. We assembled a database representing about 13,000 records for ant generic distribution from over 350 regions that cover much of the globe. Based on two models of diversity and endemicity, we identified regions where our knowledge of ant diversity is most limited, regions we have called "hotspots of discovery." A priori, such regions might be expected to be remote and untouched. Instead, we found that the hotspots of discovery are also the regions in which biodiversity is the most threatened by habitat destruction. Our results not only highlight the immediate need for conservation of the remaining natural habitats in these regions, but also the extent to which, by focusing on well-known groups such as vertebrates, we may fail to conserve the far greater diversity of the smaller species yet to be found.

CRTC2 activation in the suprachiasmatic nucleus, but not paraventricular nucleus, varies in a diurnal fashion and increases with nighttime light exposure.

Entrainment of the intrinsic suprachiasmatic nucleus (SCN) molecular clock to the light-dark cycle depends on photic-driven intracellular signal transduction responses of SCN neurons that converge on cAMP response element-binding protein (CREB)-mediated regulation of gene transcription. Characterization of the CREB coactivator proteins CREB-regulated transcriptional coactivators (CRTCs) has revealed a greater degree of differential activity-dependent modulation of CREB transactivational function than previously appreciated. In confirmation of recent reports, we found an enrichment of crtc2 mRNA and prominent CRTC2 protein expression within the SCN of adult male rats. With use of a hypothalamic organotypic culture preparation for initial CRTC2-reactive antibody characterization, we found that CRTC2 immunoreactivity in hypothalamic neurons shifted from a predominantly cytoplasmic profile under basal culture conditions to a primarily nuclear localization (CRTC2 activation) 30 min after adenylate cyclase stimulation. In adult rat SCN, we found a diurnal variation in CRTC2 activation (peak at zeitgeber time of 4 h and trough at zeitgeber time of 16-20 h) but no variation in the total number of CRTC2-immunoreactive cells. There was no diurnal variation of CRTC2 activation in the hypothalamic paraventricular nucleus, another site of enriched CRTC2 expression. Exposure of rats to light (50 lux) for 30 min during the second half of their dark (nighttime) phase produced CRTC2 activation. We observed in the SCN a parallel change in the expression of a CREB-regulated gene (FOS). In contrast, nighttime light exposure had no effect on CRTC2 activation or FOS expression in the paraventricular nucleus, nor did it affect corticosterone hormone levels. These results suggest that CRTC2 participates in CREB-dependent photic entrainment of SCN function.

Capacity and establishment rules govern the number of nonnative species in communities of ground-dwelling invertebrates.

Nonnative species are a key agent of global change. However, nonnative invertebrates remain understudied at the community scales where they are most likely to drive local extirpations. We use the North American NEON pitfall trapping network to document the number of nonnative species from 51 invertebrate communities, testing four classes of drivers. We sequenced samples using the eDNA from the sample's storage ethanol. We used AICc informed regression to evaluate how native species richness, productivity, habitat, temperature, and human population density and vehicular traffic account for continent-wide variation in the number of nonnative species in a local community. The percentage of nonnatives varied 3-fold among habitat types and over 10-fold (0%-14%) overall. We found evidence for two types of constraints on nonnative diversity. Consistent with Capacity rules (i.e., how the number of niches and individuals reflect the number of species an ecosystem can support) nonnatives increased with existing native species richness and ecosystem productivity. Consistent with Establishment Rules (i.e., how the dispersal rate of nonnative propagules and the number of open sites limits nonnative species richness) nonnatives increased with automobile traffic-a measure of human-generated propagule pressure-and were twice as common in pastures than native grasslands. After accounting for drivers associated with a community's ability to support native species (native species richness and productivity), nonnatives are more common in communities that are regularly seasonally disturbed (pastures and, potentially deciduous forests) and those experiencing more vehicular traffic. These baseline values across the US North America will allow NEON's monitoring mission to document how anthropogenic change-from disturbance to propagule transport, from temperature to trends in local extinction-further shape biotic homogenization.

The 3D-Printed Custom Elbow Prosthesis for Salvage Treatment of Complex Intra-Articular Distal Humerus Fracture Malunion.

Intra-articular fractures of the distal humerus are complex injuries that often require surgery with the goal of restoring elbow range-of-motion and function. Open reduction and internal fixation has been the preferred surgical modality; however, restoration of the medial and/or lateral columns can be complicated in fractures involving a major loss of the articular surface and bony structure. Over the past decade, 3-dimensional (3D) printing has made significant advances in the field of orthopedic surgery, specifically in guiding surgeon preoperative planning. Recently, the incorporation of 3D-printing has proven to provide a safe and reliable construct for the restoration of anatomy in complex trauma cases. We present a 47-year-old woman who sustained a complex, intra-articular distal humerus fracture with associated shearing of the capitellum that went onto malunion. Patient was treated with a patient-specific 3D-printed custom elbow prosthesis with excellent outcomes. Our goal was to shed light on the use of 3D-printing technology as a viable salvage option in treating complex, intra-articular distal humeral fractures associated with lateral condylar damage that subsequently went onto malunion.

Clinal variation in colony breeding structure and level of inbreeding in the subterranean termites Reticulitermes flavipes and R. grassei.

Social insects exhibit remarkable variation in their colony breeding structures, both within and among species. Ecological factors are believed to be important in shaping reproductive traits of social insect colonies, yet there is little information linking specific environmental variables with differences in breeding structure. Subterranean termites (Rhinotermitidae) show exceptional variation in colony breeding structure, differing in the number of reproductives and degree of inbreeding; colonies can be simple families headed by a single pair of monogamous reproductives (king and queen) or they can be extended families headed by multiple inbreeding neotenic reproductives (wingless individuals). Using microsatellite markers, we characterized colony breeding structure and levels of inbreeding in populations over large parts of the range of the subterranean termites Reticulitermes flavipes in the USA and R. grassei in Europe. Combining these new data with previous results on populations of both species, we found that latitude had a strong effect on the proportion of extended-family colonies in R. flavipes and on levels of inbreeding in both species. We examined the effect of several environmental variables that vary latitudinally; while the degree of inbreeding was greatest in cool, moist habitats in both species, seasonality affected the species differently. Inbreeding in R. flavipes was most strongly associated with climatic variables (mean annual temperature and seasonality), whereas nonclimatic variables, including the availability of wood substrate and soil composition, were important predictors of inbreeding in R. grassei. These results are the first showing that termite breeding structure is shaped by local environmental factors and that species can vary in their responses to these factors.

Solvothermal synthesis of cobalt PCP pincer complexes from [Co2(CO)8].

Treatment of [Co2(CO)8] with the ipso-substituted P(C-X)PY ligands (X = Br, Cl; R = iPr, tBu) bearing Y = NH and CH2 linkers under solvothermal conditions affords the five-coordinate Co(I) and Co(III) complexes [CoI(PCPY-R)(CO)2] and [CoIII(PCPY-R)X2]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0-3.3 µB which is consistent with a d6 intermediate spin system corresponding to two unpaired electrons. In the case of P(C-X)PY ligands (X = Br, Cl; R = tBu; Y = NH) the formation of the square planar Co(II) complex [Co(PCPNH-tBu)X] was favored. This complex gives rise to a magnetic moment of 1.8 µB being consistent with a d7 low spin system corresponding to one unpaired electron. All complexes are characterized by means of spectroscopic techniques (NMR, IR), HR-MS. Representative complexes were also characterized by X-ray crystallography. Supplementary Information: The online version contains supplementary material available at 10.1007/s00706-023-03123-x.

Temperature-habitat interactions constrain seasonal activity in a continental array of pitfall traps.

Activity density (AD), the rate at which animals collectively move through their environment, emerges as the product of a taxon's local abundance and its velocity. We analyze drivers of seasonal AD using 47 localities from the National Ecological Observatory Network (NEON) both to better understand variation in ecosystem rates like pollination and seed dispersal as well as the constraints of using AD to monitor invertebrate populations. AD was measured as volume from biweekly pitfall trap arrays (ml trap-1 14 days-1 ). Pooled samples from 2017 to 2018 revealed AD extrema at most temperatures but with a strongly positive overall slope. However, habitat types varied widely in AD's seasonal temperature sensitivity, from negative in wetlands to positive in mixed forest, grassland, and shrub habitats. The temperature of maximum AD varied threefold across the 47 localities; it tracked the threefold geographic variation in maximum growing season temperature with a consistent gap of ca. 3°C across habitats, a novel macroecological result. AD holds potential as an effective proxy for investigating ecosystem rates driven by activity. However, our results suggest that its use for monitoring insect abundance is complicated by the many ways that both abundance and velocity are constrained by a locality's temperature and plant physiognomy.

Strong influence of regional species pools on continent-wide structuring of local communities.

There is a long tradition in ecology of evaluating the relative contribution of the regional species pool and local interactions on the structure of local communities. Similarly, a growing number of studies assess the phylogenetic structure of communities, relative to that in the regional species pool, to examine the interplay between broad-scale evolutionary and fine-scale ecological processes. Finally, a renewed interest in the influence of species source pools on communities has shown that the definition of the source pool influences interpretations of patterns of community structure. We use a continent-wide dataset of local ant communities and implement ecologically explicit source pool definitions to examine the relative importance of regional species pools and local interactions for shaping community structure. Then we assess which factors underlie systematic variation in the structure of communities along climatic gradients. We find that the average phylogenetic relatedness of species in ant communities decreases from tropical to temperate regions, but the strength of this relationship depends on the level of ecological realism in the definition of source pools. We conclude that the evolution of climatic niches influences the phylogenetic structure of regional source pools and that the influence of regional source pools on local community structure is strong.

Testing the role of body size and litter depth on invertebrate diversity across six forests in North America.

Ecologists search for rules by which traits dictate the abundance and distribution of species. Here we search for rules that apply across three common taxa of litter invertebrates in six North American forests from Panama to Oregon. We use image analysis to quantify the abundance and body size distributions of mites, springtails, and spiders in 21 1-m2 plots per forest. We contrast three hypotheses: two of which focus on trait-abundance relationships and a third linking abundance to species richness. Despite three orders of magnitude variation in size, the predicted negative relationship between mean body size and abundance per area occurred in only 18% of cases, never for large bodied taxa like spiders. We likewise found only 18% of tests supported our prediction that increasing litter depth allows for high abundance; two-thirds of which occurred at a single deciduous forest in Massachusetts. In contrast, invertebrate abundance constrained species richness 76% of the time. Our results suggest that body size and habitat volume in brown food webs are rarely good predictors of variation in abundance, but that variation in diversity is generally well predicted by abundance.