Michael Addition-Elimination Ring-Opening Polymerization.

A cyclic thioenone system capable of controlled ring-opening polymerization (ROP) is presented that leverages a reversible Michael addition-elimination (MAE) mechanism. The cyclic thioenone monomers are easy to access and modify and for the first time incorporate the dynamic reversibility of MAE with chain-growth polymerization. This strategy features mild polymerization conditions, tunable functionalities, controlled molecular weights (Mn), and narrow dispersities. The obtained polythioenones exhibit excellent optical transparency and good mechanical properties and can be depolymerized to recover the original monomers. Density functional theory (DFT) calculations of model reactions offer insights into the role of monomer conformation in the polymerization process, as well as explaining divergent reactivity observed in seven-membered thiepane (TP) and eight-membered thiocane (TC) ring systems. Collectively, these findings demonstrate the feasibility of MAE mechanisms in ring-opening polymerization and provide important guidelines toward future monomer designs.

Bumble bee diet breadth increases with local abundance and phenophase duration, not intraspecific variation in body size.

Patterns of abundance across space and time, and intraspecific variation in body size, are two species attributes known to influence diet breadth and the structure of interaction networks. Yet, the relative influence of these attributes on diet breadth is often assumed to be equal among taxonomic groups, and the relationship between intraspecific variation in body size on interaction patterns is frequently neglected. We observed bee-flower interactions in multiple locations across Montana, USA, for two growing seasons and measured spatial and temporal patterns of abundance, along with interspecific and intraspecific variation in body size for prevalent species. We predicted that the association between spatial and temporal patterns of abundance and intraspecific variation in body size, and diet breadth, would be stronger for bumble bee compared to non-bumble bee species, because species with flexible diets and long activity periods can interact with more food items. Bumble bees had higher local abundance, occurred in many local communities, more intraspecific variation in body size, and longer phenophases compared to non-bumble bee species, but only local abundance and phenophase duration had a stronger positive association with the diet breadth of bumble bee compared to non-bumble bee species. Communities with a higher proportion of bumble bees also had higher intraspecific variation in body size at the network-level, and network-level intraspecific variation in body size was positively correlated with diet generalization. Our findings highlight that the association between species attributes and diet breadth changes depending on the taxonomic group, with implications for the structure of interaction networks.

Ultrastrong magnon-magnon coupling and chiral spin-texture control in a dipolar 3D multilayered artificial spin-vortex ice.

Strongly-interacting nanomagnetic arrays are ideal systems for exploring reconfigurable magnonics. They provide huge microstate spaces and integrated solutions for storage and neuromorphic computing alongside GHz functionality. These systems may be broadly assessed by their range of reliably accessible states and the strength of magnon coupling phenomena and nonlinearities. Increasingly, nanomagnetic systems are expanding into three-dimensional architectures. This has enhanced the range of available magnetic microstates and functional behaviours, but engineering control over 3D states and dynamics remains challenging. Here, we introduce a 3D magnonic metamaterial composed from multilayered artificial spin ice nanoarrays. Comprising two magnetic layers separated by a non-magnetic spacer, each nanoisland may assume four macrospin or vortex states per magnetic layer. This creates a system with a rich 16N microstate space and intense static and dynamic dipolar magnetic coupling. The system exhibits a broad range of emergent phenomena driven by the strong inter-layer dipolar interaction, including ultrastrong magnon-magnon coupling with normalised coupling rates of Δ f ν = 0.57 , GHz mode shifts in zero applied field and chirality-control of magnetic vortex microstates with corresponding magnonic spectra.

Informatics-Driven Design of Superhard B-C-O Compounds.

Materials containing B, C, and O, due to the advantages of forming strong covalent bonds, may lead to materials that are superhard, i.e., those with a Vicker's hardness larger than 40 GPa. However, the exploration of this vast chemical, compositional, and configurational space is nontrivial. Here, we leverage a combination of machine learning (ML) and first-principles calculations to enable and accelerate such a targeted search. The ML models first screen for potentially superhard B-C-O compositions from a large hypothetical B-C-O candidate space. Atomic-level structure search using density functional theory (DFT) within those identified compositions, followed by further detailed analyses, unravels on four potentially superhard B-C-O phases exhibiting thermodynamic, mechanical, and dynamic stability.

Chemical Circularity in 3D Printing with Biobased Δ-Valerolactone.

Digital Light Processing (DLP) is a vat photopolymerization-based 3D printing technology that fabricates parts typically made of chemically crosslinked polymers. The rapidly growing DLP market has an increasing demand for polymer raw materials, along with growing environmental concerns. Therefore, circular DLP printing with a closed-loop recyclable ink is of great importance for sustainability. The low-ceiling temperature alkyl-substituted δ-valerolactone (VL) is an industrially accessible biorenewable feedstock for developing recyclable polymers. In this work, acrylate-functionalized poly(δ-valerolactone) (PVLA), synthesized through the ring-opening transesterification polymerization of VL, is used as a platform photoprecursor to improve the chemical circularity in DLP printing. A small portion of photocurable reactive diluent (RD) turns the unprintable PVLA into DLP printable ink. Various photocurable monomers can serve as RDs to modulate the properties of printed structures for applications like sacrificial molds, soft actuators, sensors, etc. The intrinsic depolymerizability of PVLA is well preserved, regardless of whether the printed polymer is a thermoplastic or thermoset. The recovery yield of virgin quality VL monomer is 93% through direct bulk thermolysis of the printed structures. This work proposes the utilization of depolymerizable photoprecursors and highlights the feasibility of biorenewable VL as a versatile material platform toward circular DLP printing.

Wilderness Medical Society Clinical Practice Guidelines for Prevention and Management of Avalanche and Nonavalanche Snow Burial Accidents: 2024 Update.

To provide guidance to the general public, clinicians, and avalanche professionals about best practices, the Wilderness Medical Society convened an expert panel to revise the evidence-based guidelines for the prevention, rescue, and resuscitation of avalanche and nonavalanche snow burial victims. The original panel authored the Wilderness Medical Society Practice Guidelines for Prevention and Management of Avalanche and Nonavalanche Snow Burial Accidents in 2017. A second panel was convened to update these guidelines and make recommendations based on quality of supporting evidence.

Task-adaptive physical reservoir computing.

Reservoir computing is a neuromorphic architecture that may offer viable solutions to the growing energy costs of machine learning. In software-based machine learning, computing performance can be readily reconfigured to suit different computational tasks by tuning hyperparameters. This critical functionality is missing in 'physical' reservoir computing schemes that exploit nonlinear and history-dependent responses of physical systems for data processing. Here we overcome this issue with a 'task-adaptive' approach to physical reservoir computing. By leveraging a thermodynamical phase space to reconfigure key reservoir properties, we optimize computational performance across a diverse task set. We use the spin-wave spectra of the chiral magnet Cu2OSeO3 that hosts skyrmion, conical and helical magnetic phases, providing on-demand access to different computational reservoir responses. The task-adaptive approach is applicable to a wide variety of physical systems, which we show in other chiral magnets via above (and near) room-temperature demonstrations in Co8.5Zn8.5Mn3 (and FeGe).

Chemically Recyclable Polymer System Based on Nucleophilic Aromatic Ring-Opening Polymerization.

The development of chemically recyclable polymers with desirable properties is a long-standing but challenging goal in polymer science. Central to this challenge is the need for reversible chemical reactions that can equilibrate at rapid rates and provide efficient polymerization and depolymerization cycles. Based on the dynamic chemistry of nucleophilic aromatic substitution (SNAr), we report a chemically recyclable polythioether system derived from readily accessible benzothiocane (BT) monomers. This system represents the first example of a well-defined monomer platform capable of chain-growth ring-opening polymerization through an SNAr manifold. The polymerizations reach completion in minutes, and the pendant functionalities are easily customized to tune material properties or render the polymers amenable to further functionalization. The resulting polythioether materials exhibit comparable performance to commercial thermoplastics and can be depolymerized to the original monomers in high yields.

Effects of feeding CLOSTAT (Bacillus subtilis PB6) on the clinical health, performance, and carcass characteristics of feedlot steers1.

The objectives of this experiment were to evaluate the effects of feeding Bacillus subtilis PB6 on clinical health, performance, and carcass characteristics of feedlot steers. Bos indicus crossbred steer calves (n = 397; 342 kg initial body weight [BW]) were randomly assigned to pens by initial BW; pens (n = 24) were randomly assigned to one of two of the following experimental treatments: 1) no supplemental dietary direct-fed microbial, control (CON; n = 12 pens) or 2) 13 g/steer daily B. subtilis PB6 (CLO; CLOSTAT, Kemin Industries, Des Moines, IA; n = 12 pens). Steers were housed in 12.2 × 30.5 m soil-surfaced pens; pen served as the experimental unit. The percentage of cattle treated once or twice for bovine respiratory disease (BRD) did not differ among treatments (P ≥ 0.27); BRD mortality also did not differ between CON and CLO (P = 0.34). During the receiving period, final BW (P = 0.97), average daily gain (ADG; P = 0.91), dry matter intake (DMI; P = 0.77), and gain:feed (P = 0.79) were not different among treatments. There was a tendency (P = 0.09) for CLO-supplemented steers to be 14% more efficient from days 0 to 14 of the receiving period. Final BW, overall finishing phase ADG, and DMI did not differ by treatment (P ≥ 0.14); ADG was 0.14 kg greater for CLO than CON (P = 0.03) from days 29 to 56 of the finishing period. Gain: feed tended (P = 0.07) to be 7% greater (0.144 vs. 0.141) for CLO than CON throughout the duration of the finishing period, and 6.7% greater (P = 0.08; 0.152 for CLO vs. 0.150 for CON) for the entirety of the experiment. Carcass traits did not differ among treatments (P ≥ 0.31). The results of this experiment suggest that supplementing 13 g/steer daily B. subtilis PB6 may improve feed efficiency in feedlot cattle.

One-Pot Synthesis of Depolymerizable δ-Lactone Based Vitrimers.

A depolymerizable vitrimer that allows both reprocessability and monomer recovery by a simple and scalable one-pot two-step synthesis of vitrimers from cyclic lactones is reported. Biobased δ-valerolactone with alkyl substituents (δ-lactone) has low ceiling temperature; thus, their ring-opening-polymerized aliphatic polyesters are capable of depolymerizing back to monomers. In this work, the amorphous poly(δ-lactone) is solidified into an elastomer (i.e., δ-lactone vitrimer) by a vinyl ether cross-linker with dynamic acetal linkages, giving the merits of reprocessing and healing. Thermolysis of the bulk δ-lactone vitrimer at 200 °C can recover 85-90 wt% of the material, allowing reuse without losing value and achieving a successful closed-loop life cycle. It further demonstrates that the new vitrimer has excellent properties, with the potential to serve as a biobased and sustainable replacement of conventional soft elastomers for various applications such as lenses, mold materials, soft robots, and microfluidic devices.

Mapping the planet's critical natural assets.

Sustaining the organisms, ecosystems and processes that underpin human wellbeing is necessary to achieve sustainable development. Here we define critical natural assets as the natural and semi-natural ecosystems that provide 90% of the total current magnitude of 14 types of nature's contributions to people (NCP), and we map the global locations of these critical natural assets at 2 km resolution. Critical natural assets for maintaining local-scale NCP (12 of the 14 NCP) account for 30% of total global land area and 24% of national territorial waters, while 44% of land area is required to also maintain two global-scale NCP (carbon storage and moisture recycling). These areas overlap substantially with cultural diversity (areas containing 96% of global languages) and biodiversity (covering area requirements for 73% of birds and 66% of mammals). At least 87% of the world's population live in the areas benefitting from critical natural assets for local-scale NCP, while only 16% live on the lands containing these assets. Many of the NCP mapped here are left out of international agreements focused on conserving species or mitigating climate change, yet this analysis shows that explicitly prioritizing critical natural assets and the NCP they provide could simultaneously advance development, climate and conservation goals.

Sequestration of Ruthenium Residues via Efficient Fluorous-enyne Termination.

The creation of polymers without metal contamination remains a significant challenge for metathesis-based polymerization techniques and has complicated applications in biomedical and electronic applications. This communication reports a new approach for the removal of ruthenium byproducts through the design of an enyne terminator for metathesis polymerization that contains a fluorous tag. Upon reaction of a living polymer chain with the enyne, the ruthenium center is captured as a stable sulfur-chelated complex that can be efficiently removed after a single filtration through a fluorous cartridge. Levels of ruthenium residues as determined by ICP-MS were found to depend on the monomer structure, eluting solvent, and the degree of polymerization targeted. Ruthenium residues were minimized to low ppm levels (4-75 ppm) for most samples examined and also led to the improved thermal stability of the final materials. This represents the most efficient single method for removal of ruthenium residues from metathesis polymerization products.

Frequency dependence of the ultrasonic power reflected from the water-tissue interface of human cancellous bone in vitro.

Numerous studies have performed in vitro ultrasonic measurements of cancellous bone in water to develop techniques for ultrasonic bone assessment. Because cancellous bone is a highly porous medium, ultrasonic reflections at the water-bone interface may be frequency dependent. The goal of this study was to investigate the effect of porosity on the frequency dependence of the reflected power. Ultrasonic measurements were performed in a water tank at room temperature on 15 specimens of cancellous bone prepared from the proximal end of 9 human femurs using single element, broadband transducers with center frequencies of 3.5, 5, 7.5, and 10 MHz. Power spectra of pulses reflected from the water-specimen interface were corrected for the frequency response of the measurement system to obtain the reflected power in decibels RdB(f). To suppress random phase cancellation effects, RdB(f) was averaged over multiple sites on multiple specimens. A frequency dependence of RdB(f) was observed in the 2.6-10 MHz range. The frequency dependence was moderate, with a maximum change of less than 6 dB over the entire frequency range. RdB(f) was greatest for low porosity specimens. The frequency averaged intensity reflection coefficient ranged from 7.4 × 10-4 to 7.8 × 10-3 for high and low porosity specimen groups, respectively.

Modulating Polymerization Thermodynamics of Thiolactones Through Substituent and Heteroatom Incorporation.

A central challenge in the development of next-generation sustainable materials is to design polymers that can easily revert back to their monomeric starting material through chemical recycling to monomer (CRM). An emerging monomer class that displays efficient CRM are thiolactones, which exhibit rapid rates of polymerization and depolymerization. This report details the polymerization thermodynamics for a series of thiolactone monomers through systematic changes to substitution patterns and sulfur heteroatom incorporation. Additionally, computational studies highlight the importance of conformation in modulating the enthalpy of polymerization, leading to monomers that display high conversions to polymer at near-ambient temperatures, while maintaining low ceiling temperatures (Tc). Specifically, the combination of a highly negative enthalpy (-19.3 kJ/mol) and entropy (-58.4 J/(mol·K)) of polymerization allows for a monomer whose equilibrium polymerization conversion is very sensitive to temperature.

A Nonfunctional Halogenase Masquerades as an Aromatizing Dehydratase in Biosynthesis of Pyrrolic Polyketides by Type I Polyketide Synthases.

The bacterial modular type I polyketide synthases (PKSs) typically furnish nonaromatic lactone and lactam natural products. Here, by the complete in vitro enzymatic production of the polyketide antibiotic pyoluteorin, we describe the biosynthetic mechanism for the construction of an aromatic resorcylic ring by a type I PKS. We find that the pyoluteorin type I PKS does not produce an aromatic product, rather furnishing an alicyclic dihydrophloroglucinol that is later enzymatically dehydrated and aromatized. The aromatizing dehydratase is encoded in the pyoluteorin biosynthetic gene cluster (BGC), and its presence is conserved in other BGCs encoding production of pyrrolic polyketides. Sequence similarity and mutational analysis demonstrates that the overall structure and position of the active site for the aromatizing dehydratase is shared with flavin-dependent halogenases albeit with a loss in ability to perform redox catalysis. We demonstrate that the post-PKS dehydrative aromatization is critical for the antibiotic activity of pyoluteorin.

Cascade Alternating Metathesis Cyclopolymerization of Diynes and Dihydrofuran.

Ruthenium alkoxymethylidene complexes have recently come into view as competent species for metathesis copolymerization reactions when coupled with appropriate comonomer targets. Here, we explore the ability of Fischer-type carbenes to participate in cascade alternating metathesis cyclopolymerization (CAMC) through facile terminal alkyne addition. The combination of diyne monomers and an equal feed ratio of low-strain dihydrofuran leads to a controlled chain-growth copolymerization with high degrees of alternation (>97% alternating diads) and produces degradable polymer materials with low dispersities and targetable molecular weights. When combined with enyne monomers, this method is amenable to the synthesis of alternating diblock copolymers that can be fully degraded to short oligomer fragments under aqueous acidic conditions. This work furthers the potential for the generation of functional metathesis materials via Fischer-type ruthenium alkylidenes.

Reconfigurable training and reservoir computing in an artificial spin-vortex ice via spin-wave fingerprinting.

Strongly interacting artificial spin systems are moving beyond mimicking naturally occurring materials to emerge as versatile functional platforms, from reconfigurable magnonics to neuromorphic computing. Typically, artificial spin systems comprise nanomagnets with a single magnetization texture: collinear macrospins or chiral vortices. By tuning nanoarray dimensions we have achieved macrospin-vortex bistability and demonstrated a four-state metamaterial spin system, the 'artificial spin-vortex ice' (ASVI). ASVI can host Ising-like macrospins with strong ice-like vertex interactions and weakly coupled vortices with low stray dipolar field. Vortices and macrospins exhibit starkly differing spin-wave spectra with analogue mode amplitude control and mode frequency shifts of Δf = 3.8 GHz. The enhanced bitextural microstate space gives rise to emergent physical memory phenomena, with ratchet-like vortex injection and history-dependent non-linear fading memory when driven through global magnetic field cycles. We employed spin-wave microstate fingerprinting for rapid, scalable readout of vortex and macrospin populations, and leveraged this for spin-wave reservoir computation. ASVI performs non-linear mapping transformations of diverse input and target signals in addition to chaotic time-series forecasting.

Two-dimensional mapping of the ultrasonic attenuation and speed of sound in brain.

Brain is inhomogeneous due to its composition of different tissue types (gray and white matter), anatomical structures (e.g. thalamus and cerebellum), and cavities in the brain (ventricles). These inhomogeneities lead to spatial variations in the ultrasonic properties of the organ. The goal of this study is to characterize the spatial variation of the speed of ultrasound and frequency slope of attenuation in fixed sheep brain. 1-cm-thick slices of tissue from the coronal, sagittal and transverse cardinal planes were prepared from 12 brains. Ultrasonic measurements were performed using broadband transducers with center frequencies of 3.5, 5.0, 7.5 and 10 MHz. By mechanically scanning the transducers over the specimens, two-dimensional maps of the speed of sound (SOS) and frequency slope of attenuation (FSA) were produced. Measured values for the spatial mean and standard deviation of FSA ranged between 0.59 and 0.81 dB/cm·MHz and 0.29-0.60 dB/cm·MHz, respectively, depending on the specimen and transducer frequency. Measured values for the spatial mean and standard deviation of SOS ranged from 1532-1541 m/s and 10-14 m/s, respectively. Detailed, two-dimensional maps of FSA and SOS were produced, representing the first such characterization of the spatial variation of the ultrasonic properties of normal mammalian brain.

Amlodipine overdose complicated by non-cardiogenic pulmonary edema and diffuse alveolar hemorrhage: A case report.

A young adult female presented with hypotension and depressed mental status after intentional overdose of Amlodipine. After intubation and institution of lung-protective mechanical ventilation, initial management focused on maintenance of a mean arterial blood pressure over 65 mmHg and included fluid resuscitation (eight liters of crystalloid), Insulin and dextrose, intravenous calcium and, finally, vasopressor support. Her course was complicated by hypoxia due to non-cardiogenic pulmonary edema requiring diuresis. She was extubated soon thereafter but developed severe hypoxia within 72 hours requiring re-intubation. A subsequent bronchoscopy demonstrated diffuse alveolar hemorrhage (DAH). This is the first report of DAH complicating amlodipine overdose.