Conversion of waste poly(vinyl chloride) to branched polyethylene mediated by silylium ions.

Full dechlorination of poly(vinyl chloride) (PVC) in a controlled manner to yield useful polymeric and chlorinated products is of great interest for the processing of PVC waste. Forming polyethylene (PE) without corrosive by-products would allow for a pre-treatment of PE wastes that are often contaminated with PVC. Herein, full dechlorination of PVC has been achieved via generation of silylium ions in situ, to furnish PE products. Complete dechlorination of PVC can be achieved in 2 hours, yielding organic polymer that has similar spectroscopic and thermal signatures of branched PE, with no observable chlorine. The degree of branching can be tuned between 31 and 57 branches per 1000 carbons, with melting temperatures ranging from 51 to 93 °C. This method is applicable to not only pure PVC, but also commercial PVC products. Depending on if the PVC products are separated from plasticizers, different melting points of the resulting PE are observed. PVC dechlorination in the presence of PE waste is also shown. This is the first report of being able to cleanly convert PVC waste to PE in high yields and tune the thermal properties of the PE product, highlighting the remarkable control that silylium ion mediated transformations enables compared to past chemical methods.

Choline Halide-Based Deep Eutectic Solvents as Biocompatible Catalysts for the Alternating Copolymerization of Epoxides and Cyclic Anhydrides.

Aliphatic polyesters have received considerable attention in recent years due to their biodegradability and biocompatible, mechanical, and thermal properties that can make them a suitable alternative to today's commercialized polymers. The ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a route to synthesize a diverse array of polyesters that could be useful in many applications. However, the catalysts used rarely consider biocompatible catalysts in the case that any are left in the polymer. To the best of our knowledge, we report the first example of using deep eutectic solvents (DESs) as biocompatible catalysts for this target ROCOP with polymerization activity for at least six diverse monomer pairs. Choline halide salts are active for this polymerization, with dried salts showing polymerization slower than that of those conducted in air. Hydrogen bonding with water is hypothesized to enhance the rate-determining step of epoxide ring opening. While the presence of water improves the rate of polymerization, it also acts as a chain transfer agent, leading to smaller molar mass polymers than intended. Combining the choline halide salts with urea or ethylene glycol hydrogen bond donors in air led to DES catalysts that reacted similarly to the salts exposed to air. However, when generating these DESs in air-free conditions, they showed similar rates of polymerization without a drop in polymer molar mass. The hydrogen bonding provided by urea and ethylene glycol seems to promote the rate increase without serving as a chain transfer agent. Results reported herein display the promising potential of biocompatible catalyst systems for this ROCOP process as well as introducing the use of hydrogen bonding to enhance polymerization rates.

Assessing learning and memory among patients with pediatric brain tumor (PBT): a comparison of measures.

Patients with pediatric brain tumor (PBT) can have memory deficits due to tumor location, medical complications, and treatment. The main objective of this study was to investigate whether the California Verbal Learning Test-Children's Version (CVLT-C; 1994) and briefer Child and Adolescent Memory Profile (ChAMP; 2015) similarly identify such deficits. Seventy-five patients with PBT ages 8-16 (x‾ = 13.1 years, SD = 2.1) were administered the ChAMP or CVLT-C. Rote verbal learning, long-term retrieval, and recognition were analyzed using standardized z-scores. Analyses of differences between measures did not reach statistical significance. Both measures indicated significant downward shifts across free retrieval trials from normative means, with scores approximately 1/3 (ChAMP) to 1/2 (CVLT-C) SD below means across learning and long-term retrieval trials. Scores on recognition trials did not differ significantly from the normative mean. Post-hoc analyses using a subset of the sample who received cranial irradiation (n = 45) similarly found no significant differences between memory measures. Additional post-hoc examination of proportion of participants falling within or below the "below average" range (≤8th percentile) revealed comparable performance between the two measures, whereas the proportion of participants falling at or below 1.5 SDs below the mean on retrieval trials was lower using ChAMP Lists as compared to the CVLT-C. Given the ChAMP is less demanding in terms of time and effort and utilizes more updated and representative normative data, this study supports the ChAMP as a useful tool to evaluate learning and memory within this population.

Structural basis for Lewis antigen synthesis by the α1,3-fucosyltransferase FUT9.

Mammalian cell surface and secreted glycoproteins exhibit remarkable glycan structural diversity that contributes to numerous physiological and pathogenic interactions. Terminal glycan structures include Lewis antigens synthesized by a collection of α1,3/4-fucosyltransferases (CAZy GT10 family). At present, the only available crystallographic structure of a GT10 member is that of the Helicobacter pylori α1,3-fucosyltransferase, but mammalian GT10 fucosyltransferases are distinct in sequence and substrate specificity compared with the bacterial enzyme. Here, we determined crystal structures of human FUT9, an α1,3-fucosyltransferase that generates Lewisx and Lewisy antigens, in complex with GDP, acceptor glycans, and as a FUT9-donor analog-acceptor Michaelis complex. The structures reveal substrate specificity determinants and allow prediction of a catalytic model supported by kinetic analyses of numerous active site mutants. Comparisons with other GT10 fucosyltransferases and GT-B fold glycosyltransferases provide evidence for modular evolution of donor- and acceptor-binding sites and specificity for Lewis antigen synthesis among mammalian GT10 fucosyltransferases.

Headache in Pregnancy: Preeclampsia and Intracerebral Hemorrhage.

Preeclampsia is a type of hypertensive disorder of pregnancy that can cause significant maternal and perinatal morbidity and mortality. Hypertension and proteinuria are the keystones of the disease, though systemic end-organ dysfunction may follow. The pathogenesis is multifactorial, with known influences by placental, vascular, renal, and immunological dysfunction. This is a case of preeclampsia complicated by preterm delivery and antepartum intracerebral hemorrhage secondary to aneurysm rupture, presenting as dull headaches and blurry vision, commonly associated with severe features.

Simple yttrium salts as highly active and controlled catalysts for the atom-efficient synthesis of high molecular weight polyesters.

The ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a promising route to sustainable aliphatic polyesters with diverse mechanical and thermal properties. Here, simple yttrium chloride salts (YCl3THF3.5 and YCl3·6H2O), in combination with a bis(triphenylphosphoranylidene)ammonium chloride [PPN]Cl cocatalyst, are used as efficient and controlled catalysts for ten epoxide and anhydride combinations. In comparison to past literature, this simple salt system exhibits competitive turn-over frequencies (TOFs) for most monomer pairs. Despite no supporting ligand framework, these salts provide excellent control of dispersity, with suppression of side reactions. Using these catalysts, the highest molecular weight reported to date (302.2 kDa) has been obtained with a monosubstituted epoxide and tricyclic anhydride. These data indicate that excellent molecular weight control and suppression of side reactions for ROCOP of epoxides and cyclic anhydrides can coincide with high activity using a simple catalytic system, warranting further research in working towards industrial viability.

A Peculiar Case of Recurrent Coronary Artery Thrombosis.

Coronary artery thrombosis is a phenomenon physicians have studied throughout the years. The different risk factors that play a role in the formation of an atherosclerotic plaque leading to coronary artery blockage are vast and can affect the patient significantly if not examined and diagnosed carefully. The objective of this case report is to highlight this unusual occurrence of repeated coronary artery thrombosis. A 54-year-old Caucasian female presented to the emergency department with a one-day history of sharp chest pain in the substernal area that radiated between her shoulder blades and left arm. Despite being on dual antiplatelet therapy, an electrocardiogram (ECG) showed an inferior ST-elevation myocardial infarction (STEMI). Her medical history was extensive with factor V Leiden deficiency, hyperhomocysteinemia, recurrent deep vein thrombosis (DVT), and a family history of myocardial infarction. The patient was taken to the cardiac catheterization lab based on these characteristics. The patient was diagnosed with a 100% thrombosis in the distal right coronary artery (RCA), which was stented nine months before this current presentation. The patient had been compliant with all her medications from her previous stent placement. A new drug-eluting stent (DES) was inserted, and the patient was placed on prasugrel and apixaban. This was a very interesting topic for a case report due to the time frame of repeat thrombosis in a coronary artery with a DES and the patient's underlying hypercoagulable state. There are few cases of same vessel restenosis post-DES placement. Our case highlights the need for further research into the prevalence of genetic risk factors in coronary artery thrombosis and the need to investigate the efficacy of different anticoagulation therapies in patients with factor V Leiden thrombophilia.

Culture is reducing genetic heritability and superseding genetic adaptation.

Uchiyama et al. reveal how group-structured cultural variation influences measurements of trait heritability. We argue that understanding culture's influence on phenotypic heritability can clarify the impact of culture on genetic inheritance, which has implications for long-term gene-culture coevolution. Their analysis may provide guidance for testing our hypothesis that cultural adaptation is superseding genetic adaptation in the long term.

Inconsistent evolution and growth-survival tradeoffs in Gambusia affinis.

Growth-survival tradeoffs may be a generalizable mechanism influencing trajectories of prey evolution. Here, we investigate evolutionary contributions to growth and survival in western mosquitofish (Gambusia affinis) from 10 populations from high- and low-predation ancestral environments. We assess (i) the degree to which evolutionary components of growth and survival are consistent or inconsistent across populations within ancestral predation environments, and (ii) whether growth and survival trade off at the population level. We measure growth and survival on groups of common-reared mosquitofish in pond mesocosms. We find that evolution of growth is consistent, with fish from low-predation ancestral environments showing higher growth, while the evolution of survival is inconsistent, with significant population-level divergence unrelated to ancestral predation environment. Such inconsistency prevents a growth-survival tradeoff across populations. Thus, the generalizability of contemporary evolution probably depends on local context of evolutionary tradeoffs, and a continued focus on singular selective agents (e.g. predators) without such local context will impede insights into generalizable evolutionary patterns.

Drivers and Cascading Ecological Consequences of Gambusia affinis Trait Variation.

AbstractPhenotypic trait differences among populations can shape ecological outcomes for communities and ecosystems. However, few studies have mechanistically linked heritable and plastic components of trait variation to generalizable processes of ecology, such as trophic cascades. Here, we assess morphological and behavioral trait variation in nine populations of common garden-reared western mosquitofish (Gambusia affinis) from three distinct ancestral predator environments (three populations per environment), each reared in the presence and absence of predator cues. We then use a pond mesocosm experiment to examine the ecological consequences of mosquitofish trait variation and density variation. Our results show significant among-population trait variation, but this variation was generally unrelated to ancestral predator environment. When traits did vary congruently with respect to ancestral predator environment, this trait variation was driven by gene-by-environment interactions. Variation in several mosquitofish traits altered the cascading effects of mosquitofish on zooplankton and primary producers, but the effect of any given trait was typically weaker than that of density. We note that the relatively stronger ecological effects of density may mask the effects of traits in some systems. Our example here shows that trait variation can be highly noncongruent with respect to a perceived selective agent, phenotypic change is a product of complex interactions between genes and the environment, and numerous interacting phenotypes generate significant but potentially cryptic cascading ecological change.

Predators balance consequences of climate-change-induced habitat shifts for range-shifting and resident species.

While many species distributions are shifting poleward or up in elevation in response to a changing climate, others are shifting their habitats along localized gradients in environmental conditions as abiotic conditions become more stressful. Whether species are moving across regional or local environmental gradients in response to climate change, range-shifting species become embedded in established communities of competitors and predators. The consequences of these shifts for both resident and shifting species are often unknown, as it can be difficult to isolate the effects of multiple species interactions. Using a model system of insects in high-elevation ponds in the Rocky Mountains of Colorado, we sought to disentangle the effects of predation and intraguild interactions on the survival and development of a semi-permanent pond resident caddisfly Limnephilus externus and the habitat-shifting caddis Asynarchus nigriculus that is being forced into semi-permanent ponds as temporary ponds dry too quickly to complete development. We conducted a manipulative in-situ pond cage experiment in which L. externus and A. nigriculus caddisfly larvae in single-species treatments and together were exposed to the presence/absence of predatory Dytiscus diving beetle larvae. This approach allowed us to isolate the effects of intraguild interactions and predation on the survival and development of both the resident and habitat-shifting species. We found that intraguild interactions had strong negative effects on the resident and habitat-shifting species. Intraguild interactions reduced the survival of the resident L. externus and increased the variation in survival of the shifting A. nigriculus. However, Dytiscus predators reduced these negative effects, stabilizing the community by increasing L. externus survival and reducing variation in A. nigriculus survival. We also found that intraguild interactions reduced L. externus biomass but resulted in increased A. nigriculus development. A. nigriculus development was also increased by predation. Our results show that strong intraguild interactions between resident and shifting species are likely to have negative consequences for both species. However, the presence of predators reduces these negative consequences of the habitat shift on both the resident and the shifting.

The pace of modern life, revisited.

Wild populations must continuously respond to environmental changes or they risk extinction. Those responses can be measured as phenotypic rates of change, which can allow us to predict contemporary adaptive responses, some of which are evolutionary. About two decades ago, a database of phenotypic rates of change in wild populations was compiled. Since then, researchers have used (and expanded) this database to examine phenotypic responses to specific types of human disturbance. Here, we update the database by adding 5675 new estimates of phenotypic change. Using this newer version of the data base, now containing 7338 estimates of phenotypic change, we revisit the conclusions of four published articles. We then synthesize the expanded database to compare rates of change across different types of human disturbance. Analyses of this expanded database suggest that: (i) a small absolute difference in rates of change exists between human disturbed and natural populations, (ii) harvesting by humans results in higher rates of change than other types of disturbance, (iii) introduced populations have increased rates of change, and (iv) body size does not increase through time. Thus, findings from earlier analyses have largely held-up in analyses of our new database that encompass a much larger breadth of species, traits, and human disturbances. Lastly, we use new analyses to explore how various types of human disturbances affect rates of phenotypic change, and we call for this database to serve as a steppingstone for further analyses to understand patterns of contemporary phenotypic change.

Influence of the COVID-19 pandemic on amphibian road mortality.

The COVID-19 pandemic and its related human activity shutdowns provide unique opportunities for biodiversity monitoring through what has been termed the "anthropause" or the "great human confinement experiment." The pandemic caused immense disruption to human activity in the northeastern United States in the spring of 2020, with notable reductions in traffic levels. These shutdowns coincided with the seasonal migration of adult amphibians, which are typically subject to intense vehicle-impact mortality. Using data collected as part of an annual community science monitoring program in Maine from 2018 to 2021, we examined how amphibian mortality probabilities responded to reductions in traffic during the pandemic. While we detected a 50% decline for all amphibians, this was driven entirely by reductions in frog mortality. Wildlife collision data from the Maine Department of Transportation on other wildlife species support our finding of drastic declines in wildlife road mortality in spring 2020 when compared with immediately previous and subsequent years. Additionally, we find that frogs suffer significantly higher road mortality than salamanders, particularly when conditions are warmer and wetter.

Catalytic methods for chemical recycling or upcycling of commercial polymers.

Polymers (plastics) have transformed our lives by providing access to inexpensive and versatile materials with a variety of useful properties. While polymers have improved our lives in many ways, their longevity has created some unintended consequences. The extreme stability and durability of most commercial polymers, combined with the lack of equivalent degradable alternatives and ineffective collection and recycling policies, have led to an accumulation of polymers in landfills and oceans. This problem is reaching a critical threat to the environment, creating a demand for immediate action. Chemical recycling and upcycling involve the conversion of polymer materials into their original monomers, fuels or chemical precursors for value-added products. These approaches are the most promising for value-recovery of post-consumer polymer products; however, they are often cost-prohibitive in comparison to current recycling and disposal methods. Catalysts can be used to accelerate and improve product selectivity for chemical recycling and upcycling of polymers. This review aims to not only highlight and describe the tremendous efforts towards the development of improved catalysts for well-known chemical recycling processes, but also identify new promising methods for catalytic recycling or upcycling of the most abundant commercial polymers.

Meta-analysis: Congruence of genomic and phenotypic differentiation across diverse natural study systems.

Linking genotype to phenotype is a primary goal for understanding the genomic underpinnings of evolution. However, little work has explored whether patterns of linked genomic and phenotypic differentiation are congruent across natural study systems and traits. Here, we investigate such patterns with a meta-analysis of studies examining population-level differentiation at subsets of loci and traits putatively responding to divergent selection. We show that across the 31 studies (88 natural population-level comparisons) we examined, there was a moderate (R 2 = 0.39) relationship between genomic differentiation (F ST ) and phenotypic differentiation (P ST ) for loci and traits putatively under selection. This quantitative relationship between P ST and F ST for loci under selection in diverse taxa provides broad context and cross-system predictions for genomic and phenotypic adaptation by natural selection in natural populations. This context may eventually allow for more precise ideas of what constitutes "strong" differentiation, predictions about the effect size of loci, comparisons of taxa evolving in nonparallel ways, and more. On the other hand, links between P ST and F ST within studies were very weak, suggesting that much work remains in linking genomic differentiation to phenotypic differentiation at specific phenotypes. We suggest that linking genotypes to specific phenotypes can be improved by correlating genomic and phenotypic differentiation across a spectrum of diverging populations within a taxon and including wide coverage of both genomes and phenomes.

Long-term gene-culture coevolution and the human evolutionary transition.

It has been suggested that the human species may be undergoing an evolutionary transition in individuality (ETI). But there is disagreement about how to apply the ETI framework to our species, and whether culture is implicated as either cause or consequence. Long-term gene-culture coevolution (GCC) is also poorly understood. Some have argued that culture steers human evolution, while others proposed that genes hold culture on a leash. We review the literature and evidence on long-term GCC in humans and find a set of common themes. First, culture appears to hold greater adaptive potential than genetic inheritance and is probably driving human evolution. The evolutionary impact of culture occurs mainly through culturally organized groups, which have come to dominate human affairs in recent millennia. Second, the role of culture appears to be growing, increasingly bypassing genetic evolution and weakening genetic adaptive potential. Taken together, these findings suggest that human long-term GCC is characterized by an evolutionary transition in inheritance (from genes to culture) which entails a transition in individuality (from genetic individual to cultural group). Thus, research on GCC should focus on the possibility of an ongoing transition in the human inheritance system.

Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered.

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)5Cr(2-isocyano-1,3-X2-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime "workhorse" aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr-CNAz bond distances}, cyclic voltametric {E1/2(Cr0/1+)}, 13C NMR {δ(13CN), δ(13CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {νN≡C, νC≡O, kC≡O} analyses of the [(OC)5Cr(2-isocyano-1,3-X2-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(13COtrans) vs. δ(13CN), δ(13COcis) vs. δ(13CN), and δ(13COtrans) vs. kC≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC6F5 and CNC2F3.

Comparison of human poly-N-acetyl-lactosamine synthase structure with GT-A fold glycosyltransferases supports a modular assembly of catalytic subsites.

Poly-N-acetyl-lactosamine (poly-LacNAc) structures are composed of repeating [-Galß(1,4)-GlcNAcß(1,3)-]n glycan extensions. They are found on both N- and O-glycoproteins and glycolipids and play an important role in development, immune function, and human disease. The majority of mammalian poly-LacNAc is synthesized by the alternating iterative action of ß1,3-N-acetylglucosaminyltransferase 2 (B3GNT2) and ß1,4-galactosyltransferases. B3GNT2 is in the largest mammalian glycosyltransferase family, GT31, but little is known about the structure, substrate recognition, or catalysis by family members. Here we report the structures of human B3GNT2 in complex with UDP:Mg2+ and in complex with both UDP:Mg2+ and a glycan acceptor, lacto-N-neotetraose. The B3GNT2 structure conserves the GT-A fold and the DxD motif that coordinates a Mg2+ ion for binding the UDP-GlcNAc sugar donor. The acceptor complex shows interactions with only the terminal Galß(1,4)-GlcNAcß(1,3)- disaccharide unit, which likely explains the specificity for both N- and O-glycan acceptors. Modeling of the UDP-GlcNAc donor supports a direct displacement inverting catalytic mechanism. Comparative structural analysis indicates that nucleotide sugar donors for GT-A fold glycosyltransferases bind in similar positions and conformations without conserving interacting residues, even for enzymes that use the same donor substrate. In contrast, the B3GNT2 acceptor binding site is consistent with prior models suggesting that the evolution of acceptor specificity involves loops inserted into the stable GT-A fold. These observations support the hypothesis that GT-A fold glycosyltransferases employ coevolving donor, acceptor, and catalytic subsite modules as templates to achieve the complex diversity of glycan linkages in biological systems.

Characterizing human α-1,6-fucosyltransferase (FUT8) substrate specificity and structural similarities with related fucosyltransferases.

Mammalian Asn-linked glycans are extensively processed as they transit the secretory pathway to generate diverse glycans on cell surface and secreted glycoproteins. Additional modification of the glycan core by α-1,6-fucose addition to the innermost GlcNAc residue (core fucosylation) is catalyzed by an α-1,6-fucosyltransferase (FUT8). The importance of core fucosylation can be seen in the complex pathological phenotypes of FUT8 null mice, which display defects in cellular signaling, development, and subsequent neonatal lethality. Elevated core fucosylation has also been identified in several human cancers. However, the structural basis for FUT8 substrate specificity remains unknown.Here, using various crystal structures of FUT8 in complex with a donor substrate analog, and with four distinct glycan acceptors, we identify the molecular basis for FUT8 specificity and activity. The ordering of three active site loops corresponds to an increased occupancy for bound GDP, suggesting an induced-fit folding of the donor-binding subsite. Structures of the various acceptor complexes were compared with kinetic data on FUT8 active site mutants and with specificity data from a library of glycan acceptors to reveal how binding site complementarity and steric hindrance can tune substrate affinity. The FUT8 structure was also compared with other known fucosyltransferases to identify conserved and divergent structural features for donor and acceptor recognition and catalysis. These data provide insights into the evolution of modular templates for donor and acceptor recognition among GT-B fold glycosyltransferases in the synthesis of diverse glycan structures in biological systems.