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The rate constant of the associative ionization reaction N(2P) + O(3P) → NO+ + e− was measured using a flow tube apparatus. A flowing afterglow source was used to produce an ion/electron plasma containing a mixture of ions, including N2+, N3+, and N4+. Dissociative recombination of these species produced a population of nitrogen atoms, including N(2P). Charged species were rejected from the flow tube using an electrostatic grid, subsequent to which oxygen atoms were introduced, produced either using a discharge of helium and oxygen or via the titration of nitrogen atoms with NO. Only the title reaction can produce the NO+ observed after the introduction of O atoms. The resulting rate constant (8 ± 5 ×10−11 cm3 s−1) is larger than previously reported N(2P) + O disappearance rate constants (∼2 × 10−11 cm3 s−1). The possible errors in this or previous experiments are discussed. It is concluded that the N(2P) + O(3P) reaction proceeds almost entirely by associative ionization, with quenching to the 2D or 4S states as only minor processes. [ABSTRACT FROM AUTHOR]

It is usually asserted that physical Hamiltonians for fermions must contain an even number of fermion operators. This is indeed true in electronic structure theory. However, when the Jordan–Wigner (JW) transformation is used to map physical spin Hamiltonians to Hamiltonians of spinless fermions, terms that contain an odd number of fermion operators may appear. The resulting fermionic Hamiltonian thus does not have number parity symmetry and requires wave functions that do not have this symmetry either. In this work, we discuss the extension of standard Hartree–Fock–Bogoliubov (HFB) theory to the number-parity-nonconserving case. These ideas had appeared in the literature before but, perhaps for lack of practical applications, had, to the best of our knowledge, never been employed. We here present a useful application for this more general HFB theory based on coherent states of the SO(2M + 1) Lie group, where M is the number of orbitals. We also show how using these unusual mean-field states can provide significant improvements when studying the JW transformation of chemically relevant spin Hamiltonians. [ABSTRACT FROM AUTHOR]

We introduce Sz spin-projection based on cluster mean-field theory and apply it to the ground state of strongly correlated spin systems. In cluster mean-fields, the ground state wavefunction is written as a factorized tensor product of optimized cluster states. In previous work, we have focused on unrestricted cluster mean-field, where each cluster is Sz symmetry adapted. We here remove this restriction by introducing a generalized cluster mean-field (GcMF) theory, where each cluster is allowed to access all Sz sectors, breaking Sz symmetry. In addition, a projection scheme is used to restore global Sz, which gives rise to the Sz spin-projected generalized cluster mean-field (SzGcMF). Both of these extensions contribute to accounting for inter-cluster correlations. We benchmark these methods on the 1D, quasi-2D, and 2D J1 − J2 and XXZ Heisenberg models. Our results indicate that the new methods (GcMF and SzGcMF) provide a qualitative and semi-quantitative description of the Heisenberg lattices in the regimes considered, suggesting them as useful references for further inter-cluster correlations, which are discussed in this work. [ABSTRACT FROM AUTHOR]

The rate constant for electron attachment to Mo(CO)6 was determined to be ka = 2.4 ± 0.6 × 10−7 cm3 s−1 at 297 K in a flowing-afterglow Langmuir-probe experiment. The sole anion product is Mo(CO)5−. A small decline in ka was observed up to 450 K, and decomposition was apparent at higher temperatures. The charge transfer reaction of Ar+ with Mo(CO)6 is exothermic by 7.59 ± 0.03 eV, which appears to be sufficient to remove the first 5 ligands from Mo(CO)6+. [ABSTRACT FROM AUTHOR]

The Hosmer-Lemeshow (HL) test is a commonly used global goodness-of-fit (GOF) test that assesses the quality of the overall fit of a logistic regression model. In this paper, we give results from simulations showing that the type I error rate (and hence power) of the HL test decreases as model complexity grows, provided that the sample size remains fixed and binary replicates (multiple Bernoulli trials) are present in the data. We demonstrate that a generalized version of the HL test (GHL) presented in previous work can offer some protection against this power loss. These results are also supported by application of both the HL and GHL test to a real-life data set. We conclude with a brief discussion explaining the behavior of the HL test, along with some guidance on how to choose between the two tests. In particular, we suggest the GHL test to be used when there are binary replicates or clusters in the covariate space, provided that the sample size is sufficiently large. [ABSTRACT FROM AUTHOR]

With a multitude of options for pulmonary embolism management, we review the most common diagnostic tools available for assessing risk as well as how each broad risk category is typically treated. Right heart dysfunction is the cornerstone for triage of these patients and should be the focus for decision-making, especially in challenging patients. We aim to provide a modern, clinical perspective for PE management in light of the multitude of intervention options. [ABSTRACT FROM AUTHOR]

This article, titled "Pulmonary Embolism and Cardiovascular Care: Revolutionary Advances for the Decade Ahead," provides an overview of the current state of care for pulmonary embolism (PE) and explores new possibilities for reducing its impact. The article emphasizes the importance of timely diagnosis and management by a team of specialists, including the use of artificial intelligence for improved triage and diagnosis. It also discusses different diagnostic tools, risk assessment, and management approaches for PE. Additionally, the article highlights innovative treatment strategies, such as catheter interventions and balloon pulmonary angioplasty, and the importance of a multidisciplinary team for managing chronic thromboembolic pulmonary hypertension. Overall, the article offers hope for revolutionary advances in the care of PE in the coming decade. [Extracted from the article]

The updated 2024 European Association of Urology neurourology guidelines highlight the importance of a tailored, comprehensive approach for management of neurourological disorders. Patient outcomes can be improved by addressing individual needs, including urodynamics and lifestyle considerations via a multidisciplinary strategy. The guidelines cover the latest evidence and treatments to support patients in maintaining their quality of life across all facets of neurological impact. Most patients with neurourological disorders require lifelong medical care. The European Association of Urology (EAU) regularly updates guidelines for diagnosis and treatment of these patients. The objective of this review is to provide a summary of the 2024 updated EAU guidelines on neurourology. A structured literature review covering the timeframe 2021–2023 was conducted for the guideline update. A level of evidence and a strength rating were assigned for each recommendation on the basis of the literature data. Neurological conditions significantly affect urinary, sexual, and bowel function, and lifelong management is required for neurourological patients to maintain their quality of life and prevent urinary tract deterioration. Early diagnosis and effective treatment are key, and comprehensive clinical assessments, including urodynamics, are crucial. Management should be customised to individual needs and should involve a multidisciplinary approach and address sexuality and fertility. Lifelong monitoring and follow-up highlight the importance of continuous care for neurourological patients. The 2024 EAU guidelines on neurourology provide an up-to-date overview of available evidence on diagnosis, treatment, and follow-up for neurourological patients. Neurological disorders very frequently affect the lower urinary tract and sexual and bowel function and patients need lifelong management. We summarise the updated European Association of Urology guidelines on neurourology to provide patients and caregivers with the latest insights for optimal health care support. [ABSTRACT FROM AUTHOR]

ObjectiveMethodsResultsConclusionsAlthough the significance of the general factor of psychopathology (p) is being increasingly recognized, it remains unclear how to best operationalize and measure p. To test variations in the operationalizations of p and make practical recommendations for its assessment, we compared p-factor scores derived from four models.We compared p scores derived from principal axis (Model 1), hierarchical factor (Model 2), and bifactor (Model 3) analyses, plus a Total Problem score (sum of unit-weighted ratings of all problem items; Model 4) for parent- and self-rated youth psychopathology from 24 societies. Separately for each sample, we fitted the models to parent-ratings on the Child Behavior Checklist for Ages 6–18 (CBCL/6–18) and self-ratings on the Youth Self-Report (YSR) for 25,643 11–18-year-olds. Separately for each sample, we computed correlations between p-scores obtained for each pair of models, cross-informant correlations between p-scores for each model, and Q-correlations between mean item x p-score correlations for each pair of models.Results were similar for all models, as indicated by correlations of .973–.994 between p-scores for Models 1–4, plus similar cross-informant correlations between CBCL/6–18 and YSR Model 1–4 p-scores. Item x p correlations had similar rank orders between Models 1–4, as indicated by Q correlations of .957–.993.The similar results obtained for Models 1–4 argue for using the simplest model – the unit-weighted Total Problem score – to measure p for clinical and research assessment of youth psychopathology. Practical methods for measuring p may advance the field toward transdiagnostic patterns of problems. [ABSTRACT FROM AUTHOR]

Variation in the strength of synapses can be quantified by measuring the anatomical properties of synapses. Quantifying precision of synaptic plasticity is fundamental to understanding information storage and retrieval in neural circuits. Synapses from the same axon onto the same dendrite have a common history of coactivation, making them ideal candidates for determining the precision of synaptic plasticity based on the similarity of their physical dimensions. Here, the precision and amount of information stored in synapse dimensions were quantified with Shannon information theory, expanding prior analysis that used signal detection theory (Bartol et al., 2015). The two methods were compared using dendritic spine head volumes in the middle of the stratum radiatum of hippocampal area CA1 as well-defined measures of synaptic strength. Information theory delineated the number of distinguishable synaptic strengths based on nonoverlapping bins of dendritic spine head volumes. Shannon entropy was applied to measure synaptic information storage capacity (SISC) and resulted in a lower bound of 4.1 bits and upper bound of 4.59 bits of information based on 24 distinguishable sizes. We further compared the distribution of distinguishable sizes and a uniform distribution using Kullback-Leibler divergence and discovered that there was a nearly uniform distribution of spine head volumes across the sizes, suggesting optimal use of the distinguishable values. Thus, SISC provides a new analytical measure that can be generalized to probe synaptic strengths and capacity for plasticity in different brain regions of different species and among animals raised in different conditions or during learning. How brain diseases and disorders affect the precision of synaptic plasticity can also be probed. [ABSTRACT FROM AUTHOR]

Summary Combination checkpoint inhibitor (CPI) and chemotherapy is an effective and safe treatment strategy for patients with untreated classic Hodgkin lymphoma. Recent studies of programmed cell death protein 1 inhibitors combined with doxorubicin, vinblastine and dacarbazine have demonstrated high overall and complete response rates. This combination has a unique toxicity profile that should be managed appropriately so as not to compromise treatment efficacy. Common toxicities include rash, hepatoxicity, neutropenia and thyroid dysfunction. Here, we present four cases and the management strategies around such toxicities. In addition, we highlight key clinical decision‐making around the administration of subsequent doses of CPI and chemotherapy. [ABSTRACT FROM AUTHOR]

The article discusses the launch of the funding opportunities by the National Institute on Aging (NIA) targeting clinician-scientists focused on aging research from a diverse array of specialties and disciplines. Topics include the Grants for Early Medical and Surgical Specialists' Transition to Aging Research (GEMSSTAR) initiative of the NIA, the expansion made by the NIA on its commitment to support a wider range of clinician-scientists, and the infrastructure grant launched by the NIA.

Antipredator behaviors are often crucial for animal survival. In environments impacted by humans, animals may be exposed to a wide array of chemical contaminants due to agriculture, industry, and other activities. Among other effects, these chemical contaminants may influence behaviors prey animals use to cope with predation risk, likely reducing survival by suppressing or even maladaptively reversing normal behavioral responses. Changes in behavioral responses could be the result of impaired detection of cues that indicate predator presence or altered behavioral plasticity in response to predator cues. In a laboratory experiment, we tested the effects of the commonly used herbicide metolachlor on the behavior of tadpoles of the American bullfrog (Lithobates catesbeianus) in both the absence and presence of water conditioned with cues (odor) of fish. We observed several behaviors in the tadpoles reflective of predator avoidance when exposed to combinations of metolachlor (0 or 80 ppb) and the presence or absence of fish cues. We found that metolachlor had size-dependent effects on tadpole activity levels, with larger tadpoles being much less active in the absence of metolachlor but similar in activity to small tadpoles when metolachlor was present. Fish cues similarly had size-dependent effects on multiple tadpole behaviors. Finally, hiding behavior and zone change (movement) behavior of tadpoles in response to fish cues varied depending on the presence of metolachlor and, in the case of zone changes, tadpole size. Our findings indicate that the presence of chemical contaminants has the potential to alter important antipredator behaviors. However, these effects are complex, and size may mediate the nature of the response to both chemical contaminants and predators. The herbicide metolachlor alters tadpole behavior, sometimes interactively with fish cues. Body size of tadpoles influenced the effects of metolachlor and fish. [ABSTRACT FROM AUTHOR]

The Bali myna Leucopsar rothschildi has long suffered heavy trapping, leading to its near extinction in the wild and categorization as Critically Endangered on the IUCN Red List. Decades of conservation breeding, release of birds and post-release management at Bali Barat National Park have, until recently, failed to secure a viable wild population. However, over the past decade, population increases, expansion into new areas of the National Park and beyond, and successful breeding in both artificial and natural nest sites have occurred. These recent successes are associated with a change in approach by the National Park authority from concentrating efforts on the last refugium of the species (an area protected from trapping but with potentially suboptimal habitat) and towards the human-dominated landscapes around the main road through the National Park. Bali mynas tended to favour areas with extensive shorter grass cover and open canopies and to shun denser woodland. Anthropogenic landscapes such as farmland and plantations presumably mimic the original savannah habitat of the species, but nestbox provision has probably been crucial in these areas in the absence of natural cavities. A potential further factor in the increases in myna numbers and range has been a scheme involving local people in commercial breeding of the species, thereby reducing its market price, and working with communities to reduce trapping pressure. We encourage continuing operation of this management strategy inside the National Park and its further extension into adjacent tourist areas, which appear to have myna-friendly socio-ecological conditions. [ABSTRACT FROM AUTHOR]

Our objective was to calculate the time in the sun necessary to maintain existing 25‐hydroxyvitamin D (25(OH)D) concentration at locations across Australia and New Zealand. We used a microsimulation model to estimate changes in monthly 25(OH)D concentration using data on standard erythemal dose, solar zenith angle, and climatological ozone. We estimated the number of standard vitamin D doses per 10‐min interval and used a dose‐response equation to determine the average time in the sun to maintain existing 25(OH)D concentration according to month and time of day. Across all locations in summer, 5–10 min outdoors between 8 a.m. and 4 p.m. on most days of the week, with 35% of the body surface area exposed, is sufficient to maintain existing 25(OH)D concentration. In winter, at mid‐to‐high latitudes, time outdoors during the middle of the day is required. In winter, with 10% of the body surface area exposed, greater than 45 min in the middle of the day is required in most locations to maintain existing 25(OH)D concentration. These data can be used to inform guidelines regarding maintaining vitamin D via sun exposure and may help health practitioners identify patients who may be vitamin D deficient. [ABSTRACT FROM AUTHOR]

We study epidemic spreading in complex networks by a multiple random walker approach. Each walker performs an independent simple Markovian random walk on a complex undirected (ergodic) random graph where we focus on the Barabási–Albert (BA), Erdös–Rényi (ER), and Watts–Strogatz (WS) types. Both walkers and nodes can be either susceptible (S) or infected and infectious (I), representing their state of health. Susceptible nodes may be infected by visits of infected walkers, and susceptible walkers may be infected by visiting infected nodes. No direct transmission of the disease among walkers (or among nodes) is possible. This model mimics a large class of diseases such as Dengue and Malaria with the transmission of the disease via vectors (mosquitoes). Infected walkers may die during the time span of their infection, introducing an additional compartment D of dead walkers. Contrary to the walkers, there is no mortality of infected nodes. Infected nodes always recover from their infection after a random finite time span. This assumption is based on the observation that infectious vectors (mosquitoes) are not ill and do not die from the infection. The infectious time spans of nodes and walkers, and the survival times of infected walkers, are represented by independent random variables. We derive stochastic evolution equations for the mean-field compartmental populations with the mortality of walkers and delayed transitions among the compartments. From linear stability analysis, we derive the basic reproduction numbers R M , R 0 with and without mortality, respectively, and prove that R M < R 0 . For R M , R 0 > 1 , the healthy state is unstable, whereas for zero mortality, a stable endemic equilibrium exists (independent of the initial conditions), which we obtained explicitly. We observed that the solutions of the random walk simulations in the considered networks agree well with the mean-field solutions for strongly connected graph topologies, whereas less well for weakly connected structures and for diseases with high mortality. Our model has applications beyond epidemic dynamics, for instance in the kinetics of chemical reactions, the propagation of contaminants, wood fires, and others. [ABSTRACT FROM AUTHOR]

Background Purpose Methods Results Conclusions Data‐driven gated (DDG) PET has gained clinical acceptance and has been shown to match or outperform external‐device gated (EDG) PET. However, in most clinical applications, DDG PET is matched with helical CT acquired in free breathing (FB) at a random respiratory phase, leaving registration, and optimal attenuation correction (AC) to chance. Furthermore, DDG PET requires additional scan time to reduce image noise as it only preserves 35%–50% of the PET data at or near the end‐expiratory phase of the breathing cycle.A new full‐counts, phase‐matched (FCPM) DDG PET/CT was developed based on a low‐dose cine CT to improve registration between DDG PET and DDG CT, to reduce image noise, and to avoid increasing acquisition times in DDG PET.A new DDG CT was developed for three respiratory phases of CT images from a low dose cine CT acquisition of 1.35 mSv for a coverage of about 15.4 cm: end‐inspiration (EI), average (AVG), and end‐expiration (EE) to match with the three corresponding phases of DDG PET data: −10% to 15%; 15% to 30%, and 80% to 90%; and 30% to 80%, respectively. The EI and EE phases of DDG CT were selected based on the physiological changes in lung density and body outlines reflected in the dynamic cine CT images. The AVG phase was derived from averaging of all phases of the cine CT images. The cine CT was acquired over the lower lungs and/or upper abdomen for correction of misregistration between PET and FB CT as well as DDG PET and FB CT. The three phases of DDG CT were used for AC of the corresponding phases of PET. After phase‐matched AC of each PET dataset, the EI and AVG PET data were registered to the EE PET data with deformable image registration. The final result was FCPM DDG PET/CT which accounts for all PET data registered at the EE phase. We applied this approach to 14 18F‐FDG lung cancer patient studies acquired at 2 min/bed position on the GE Discovery MI (25‐cm axial FOV) and evaluated its efficacy in improved quantification and noise reduction.Relative to static PET/CT, the SUVmax increases for the EI, AVG, EE, and FCPM DDG PET/CT were 1.67 ± 0.40, 1.50 ± 0.28, 1.64 ± 0.36, and 1.49 ± 0.28, respectively. There were 10.8% and 9.1% average decreases in SUVmax from EI and EE to FCPM DDG PET/CT, respectively. EI, AVG, and EE DDG PET/CT all maintained increased image noise relative to static PET/CT. However, the noise levels of FCPM and static PET were statistically equivalent, suggesting the inclusion of all counts was able to decrease the image noise relative to EI and EE DDG PET/CT.A new FCPM DDG PET/CT has been developed to account for 100% of collected PET data in DDG PET applications. Image noise in FCPM is comparable to static PET, while small decreases in SUVmax were also observed in FCPM when compared to either EI or EE DDG PET/CT. [ABSTRACT FROM AUTHOR]

Diffusion within extracellular matrix is essential to deliver nutrients and larger metabolites to the avascular region of the meniscus. It is well known that both structure and composition of the meniscus vary across its regions; therefore, it is crucial to fully understand how the heterogenous meniscal architecture affects its diffusive properties. The objective of this study was to investigate the effect of meniscal region (core tissue, femoral, and tibial surface layers) and molecular weight on the diffusivity of several molecules in porcine meniscus. Tissue samples were harvested from the central area of porcine lateral menisci. Diffusivity of fluorescein (MW 332 Da) and three fluorescence-labeled dextrans (MW 3k, 40k, and 150k Da) was measured via fluorescence recovery after photobleaching. Diffusivity was affected by molecular size, decreasing as the Stokes' radius of the solute increased. There was no significant effect of meniscal region on diffusivity for fluorescein, 3k and 40k dextrans (p>0.05). However, region did significantly affect the diffusivity of 150k Dextran, with that in the tibial surface layer being larger than in the core region (p = 0.001). Our findings contribute novel knowledge concerning the transport properties of the meniscus fibrocartilage. This data can be used to advance the understanding of tissue pathophysiology and explore effective approaches for tissue restoration. [ABSTRACT FROM AUTHOR]

AbstractObjectiveDesignStudy sampleResultsConclusionThis study aimed to investigate the connection between psychological factors and postoperative tinnitus in vestibular schwannoma (VS) patients following retrosigmoid microsurgery.Cross-sectional study.Ninety-three VS patients participated, completing questionnaires on demographics, tinnitus severity (THI-12), personality traits (TIPI-G), dizziness impact (DHI), perceived health benefits (GBI), somatisation tendencies (SOMS-2), and psychological distress (HADS-D). Our analysis involved Mann-Whitney U-tests, Spearman’s rank-order correlations, and false discovery rate correction.Most participants reported postoperative tinnitus (77/93), with 41 experiencing it preoperatively. Emotional stability correlated negatively with tinnitus presence, while tinnitus severity was associated with emotional distress. Preoperative somatisation tendencies were also positively linked to tinnitus severity. Postoperative Tinnitus was further linked to reduced perceived health benefits and increased anxiety and depression levels. Notably, age and gender showed no significant associations.This study uncovers the interplay between postoperative tinnitus and psychological factors in VS patients, highlighting emotional and cognitive dimensions. Tailored psychological interventions addressing tinnitus‘s psychosomatic impact may enhance patients quality of life. [ABSTRACT FROM AUTHOR]

One of the main burdens in the treatment of diseases is imputable to the delay between the appearance of molecular dysfunctions in the first affected disease cells and their presence in sufficient number for detection in specific tissues or organs. This delay obviously plays in favor of disease progression to an extent that makes efficient treatments difficult, as they arrive too late. The development of a novel medical strategy, termed cell-based interception and precision medicine, seeks to identify dysfunctional cells early, when tissue damages are not apparent and symptoms not yet present, and develop therapies to treat diseases early. Central to this strategy is the use of single-cell technologies that allow detection of molecular changes in cells at the time of phenotypical bifurcation from health to disease. In this article we describe a general procedure to support such an approach applied to neurodegenerative disorders. This procedure combines four components directed towards highly complementary objectives: 1) a high-performance single-cell proteomics (SCP) method (Detect), 2) the development of disease experimental cell models and predictive computational models of cell trajectories (Understand), 3) the discovery of specific targets and personalized therapies (Cure), and 4) the creation of a community of collaborating laboratories to accelerate the development of this novel medical paradigm (Collaborate). A global initiative named 37TrillionCells (37TC) was launched to advance the development of cell-based interception and precision medicine. [ABSTRACT FROM AUTHOR]

Over the last few years, numerous states and school boards have passed laws aimed at limiting curricula related to diverse communities. Anti-Critical Race Theory and "Don't Say Gay" laws have threatened to restrict the teaching of race and LGBTQ issues in K-12 schools. These laws are troubling from a policy standpoint because inclusive curricula ensure that students receive a proper education and are taught in a supportive school environment. They are also likely an infringement upon a student's First Amendment right to receive information, first recognized in Board of Education v. Pico, and, as such, courts have begun to entertain constitutional claims against curricular restrictions. However, there is no binding precedent on this issue, and the circuits are split as to what standard they should use when addressing these challenges. This Note argues that courts should follow the approach developed by the Ninth Circuit in Arce v. Douglas. Courts should extend Pico beyond its library context to hold that students have a First Amendment right to receive information in the curriculum they are taught. In evaluating whether a curriculum decision violates this right, courts should apply the standard laid out in Hazelwood School District v. Kuhlmeier: Courts should first require that state and local educational bodies justify that their curriculum restriction decisions were motivated by a "legitimate pedagogical concern" and courts should then inquire if such restrictions are "reasonably related" to that concern. This standard properly respects the deference states and localities are due in educational matters, while protecting students' constitutional free speech rights. The standard also follows basic requirements of constitutional law: requiring justifications, reasonableness in those justifications, and proper process. [ABSTRACT FROM AUTHOR]

The Jordan–Wigner transformation is a powerful tool for converting systems of spins into systems of fermions, or vice versa. While this mapping is exact, the transformation itself depends on the labelling of the spins. One consequence of this dependence is that approximate solutions of a Jordan–Wigner-transformed Hamiltonian may depend on the (physically inconsequential) labelling of the spins. In this work, we turn to an extended Jordan–Wigner transformation which remedies this problem and which may also introduce some correlation atop the Hartree–Fock solution of a transformed spin Hamiltonian. We demonstrate that this extended Jordan–Wigner transformation can be thought of as arising from a unitary version of the Lie algebraic similarity transformation (LAST) theory. We show how these ideas, particularly in combination with the standard (non-unitary) version of LAST, can provide a potentially powerful tool for the treatment of the XXZ and $ J_1-J_2 $ J 1 − J 2 Heisenberg Hamiltonians. [ABSTRACT FROM AUTHOR]

Research on the nature and processes of intrapersonal communication (e.g., self-talk, internal dialogues, etc.) have mainly utilized non-experimental methods. Correlational studies do not permit the examination of possible causal links between self-talk/internal dialogue and other psychological concepts. The present study provides an example of an experimental approach to studying intrapersonal communication. We test the role of self-talk under conditions of cognitive disruption, anxiety, and sadness using a 2 (pre/post) X 4 (condition) mixed methods design (N = 211). Following an initial assessment of self-talk, we randomly assigned participants to one of four recall groups: a recent situation when they experienced cognitive disruption, anxiety, or sadness, or a control condition. The experimental groups recalled their self-talk during the time the event occurred, while the control group reported their current self-talk again. Results indicated participants in the anxiety and sadness conditions reported significantly greater self-talk than the control condition. In addition, typical levels of self-talk frequency (particularly self-critical self-talk) were related to several variables, such as cognitive disruption and intrusive thoughts. The results are consistent with previous findings on the relationship between self-talk/internal dialogues and anxiety and negative emotions. We discuss ways that similar methods might be used to facilitate further experimental studies with Dialogical Self Theory. [ABSTRACT FROM AUTHOR]

We report the results of the characterization of the electrical resistivity of selected ceramic materials, namely aluminum nitride (AlN), silicon nitride (Si3N4), beryllium oxide (BeO), yttrium oxide (Y2O3), and non-ceramic silicon dioxide (SiO2), which are candidates for packaging silicon carbide (SiC) sensors and electronics that can operate at temperatures beyond 800°C. Samples of thesematerials were thermally cycled twice to 1200°C in nitrogen while the bulk and surface resistivities were measured in situ. Although the resistivity values of all samples dropped with increasing temperature, BeO maintained the relatively highest bulk and surface resistivity values at 1200°C of 28 and 34 kΩ cm, respectively, while AlN had the lowest values at 6.8 and 0.64 kΩ cm. In terms of viability for packaging SiC sensors for >800°C operation, AlN and Si3N4 are the choice candidates due to their lowest mismatches in the coefficient of thermal expansion with SiC. However, the relative resistivity stability of Si3N4 over AlN makes it a promising candidate, even with its lower thermal conductivity relative to AlN. [ABSTRACT FROM AUTHOR]

This paper assesses the performance of the Supreme Court as democratic guardrail during five prior periods of democratic crisis in the United States. It finds that most such periods witnessed efforts by the governing regime to entrench themselves in power, and that the Court has rarely provided an effective check on such democratic abuses. Rather than serving as a reliable democratic guardrail, the Court has regularly exercised what Dixon and Landau call "weak‐form abusive judicial review"; that is, it has declined to check attacks on democracy emerging from other centers of power. On one occasion, the Court has undermined democracy even more directly via "strong‐form abusive judicial review"; that is, the Court itself attacked key democratic guardrails. This historical record provides a helpful baseline for evaluating the Court's performance during the Trump era, when it has taken actions that both protect and undermine democratic health. Conflicting signs indicate that the Court is playing a more democracy‐protective role than most of its predecessors in some respects, but a more democracy‐undermining role in others. As such, it is too soon to say with confidence whether the contemporary Court will be remembered, on balance, for resolving or exacerbating a system‐threatening constitutional crisis. [ABSTRACT FROM AUTHOR]

The present work reports experimental data for the thermal conductivity of glycerol which is an important fluid in many technical applications. Measurements were performed in an absolute way at ambient pressure using a steady-state guarded parallel-plate instrument (GPPI) with an average expanded (k = 2) measurement uncertainty of 2.3%. For data representation over a temperature range from (268.15 to 363.15) K in steps of 5 K, the thermal conductivities are averaged from measurements at three different temperature gradients for each temperature. The present results indicate an almost constant thermal conductivity of glycerol over the studied temperature range and agree with the sparse experimental data available in the literature. Based on the experimental database including the results from this work, a simple correlation for the thermal conductivity of glycerol at 0.1 MPa as a function of temperature between (268 and 413) K is suggested. The additional study on the influence of water as possible contamination up to water mass fractions of 0.02 on the thermal conductivity of glycerol reveals negligible changes. Overall, the experimental results from this work contribute to an improved data situation for the thermal conductivity of glycerol, particularly in the subcooled liquid region at temperatures below 283 K. [ABSTRACT FROM AUTHOR]

The present article summarizes experimental and theoretical considerations required for a proper use of dynamic light scattering (DLS) for the measurement of transport properties of fluids. It addresses not only recent advancements of the method, but also aims to provide recommendations to researchers who intend to apply the technique in the future. As outlined in this study, DLS is based on the analysis of scattered light governed by microscopic statistical or periodic fluctuations that originate from the thermal movement of molecules and/or particles at macroscopic thermodynamic equilibrium. The dynamics of these hydrodynamic fluctuations in the bulk of fluids or at their phase boundaries are related to the underlying diffusive processes and, thus, to the associated transport properties, and are reflected by the time-dependent correlation function of the scattered light intensity. The fundamentals of this type of detection, known as photon correlation spectroscopy (PCS), will be discussed in the present contribution in some more detail. It is emphasized that the experiments need to be designed carefully in accordance with theory in order to assign the measurement signals to the corresponding hydrodynamic fluctuations. If the necessary conditions are fulfilled, DLS allows the accurate determination of several transport properties including kinematic and dynamic viscosity, thermal diffusivity, mutual diffusivity, and sound attenuation, which may be accessed together with other thermophysical properties such as speed of sound and surface or interfacial tension. In some instances, also the simultaneous determination of several transport properties is possible. With the exception of the sound attenuation, expanded uncertainties for the mentioned transport properties down to 1 % can be achieved for various types of fluid systems over a wide range of thermodynamic states up to elevated temperatures and pressures as well as in the vicinity of critical points. This performance and versatility of the DLS technique is documented in the present study by highlighting measurement examples from recent thermophysical property research on different classes of working fluids relevant for process and energy technology. [ABSTRACT FROM AUTHOR]

Context: Athletes with a history of sport concussion (SC) have an increased risk of musculoskeletal injury (MSK); however, the underlying mechanisms have yet to be determined. The purpose of our study was to evaluate kinesiophobia in college athletes with or without a time-loss MSK within 180 days of unrestricted return to play following a SC. Design: This was a retrospective cohort study within a sports medicine facility. Methods: Participants were eligible if they were diagnosed with a SC, completed the Tampa Scale of Kinesiophobia (TSK), and completed an unrestricted return to play. Fifty-six college athletes (40 men and 16 women) with an average age of 19.5 (1.25) years, height of 183.5 (10.45) cm, and mass of 94.72 (24.65) kg, were included in the study. MSK participants were matched to non-MSK participants 1:1. Demographic and TSK outcome scores were compared using independent t tests. The proportion of participants in each group who scored above the clinical threshold (TSK ≥ 37) was compared using a chi-square analysis. Alpha was set at α =.05. Results: The MSK group (31.2 [6.30]) reported similar TSK scores to the matched group (28.9 [3.34]; t54 = 1.70, P =.10, d = 0.45 [ − 0.08 to 0.97]). A greater proportion of athletes who were diagnosed with an MSK-reported scores above the cutoff (χ2[1] = 6.49, P =.01). Conclusions: Athletes diagnosed with SC had similar kinesiophobia values regardless of MSK status. However, a higher proportion of athletes with a time-loss MSK injury reported a TSK score greater than the clinical cutoff. Our results suggest that factors such as kinesiophobia should be considered following a SC. [ABSTRACT FROM AUTHOR]

The Jordan–Wigner transformation establishes a duality between su(2) and fermionic algebras. We present qualitative arguments and numerical evidence that when mapping spins to fermions, the transformation makes strong correlation weaker, as demonstrated by the Hartree–Fock approximation to the transformed Hamiltonian. This result can be rationalized in terms of rank reduction of spin shift terms when transformed to fermions. Conversely, the mapping of fermions to qubits makes strong correlation stronger, complicating its solution when one uses qubit-based correlators. The presence of string operators poses challenges to the implementation of quantum chemistry methods on classical computers, but these can be dealt with using established techniques of low computational cost. Our proof of principle results for XXZ and J1-J2 Heisenberg (in 1D and 2D) indicates that the JW transformed fermionic Hamiltonian has reduced complexity in key regions of their phase diagrams and provides a better starting point for addressing challenging spin problems. [ABSTRACT FROM AUTHOR]

Objective. Clinical outcomes after proton therapy have shown some variability that is not fully understood. Different approaches have been suggested to explain the biological outcome, but none has yet provided a comprehensive and satisfactory rationale for observed toxicities. The relatively recent transition from passive scattering (PS) to pencil beam scanning (PBS) treatments has significantly increased the voxel-wise dose rate in proton therapy. In addition, the dose rate distribution is no longer uniform along the cross section of the target but rather highly heterogeneous, following the spot placement. We suggest investigating dose rate as potential contributor to a more complex proton RBE model. Approach. Due to the time structure of the PBS beam delivery the instantaneous dose rate is highly variable voxel by voxel. Several possible parameters to represent voxel-wise dose rate for a given clinical PBS treatment plan are detailed. These quantities were implemented in the scripting environment of our treatment planning system, and computations experimentally verified. Sample applications to treated patient plans are shown. Main results. Computed dose rates we experimentally confirmed. Dose rate maps vary depending on which method is used to represent them. Mainly, the underlying time and dose intervals chosen determine the topography of the resultant distributions. The maximum dose rates experienced by any target voxel in a given PBS treatment plan in our system range from ∼100 to ∼450 Gy(RBE)/min, a factor of 10–100 increase compared to PS. These dose rate distributions are very heterogeneous, with distinct hot spots. Significance. Voxel-wise dose rates for current clinical PBS treatment plans vary greatly from clinically established practice with PS. The exploration of different dose rate measures to evaluate potential correlations with observed clinical outcomes is suggested, potentially adding a missing component in the understanding of proton relative biological effectiveness (RBE). [ABSTRACT FROM AUTHOR]

This work reports on a battery of coordination compounds featuring a versatile dianionic luminophore adopting three different coordination modes (mono, bi, and tridentate) while chelating Pd(II), Pt(II), Au(III), and Hg(II) centers. An in‐depth structural characterization of the ligand precursor (H2L) and six transition metal complexes ([HLPdCNtBu], [LPtCl], [LPtCNtBu], [LPtCNPhen], [HLHgCl], and [LAuCl]) is presented. The influence of the cations and coordination modes of the luminophore and co‐ligands on the photophysical properties (including photoluminescence quantum yields (ΦL), excited state lifetimes (τ), and average (non‐)radiative rate constants) are evaluated at various temperatures in different phases. Five complexes show interesting photophysical properties at room temperature (RT) in solution. Embedment in frozen glassy matrices at 77 K significantly boosts their luminescence by suppressing radiationless deactivation paths. Thus, the Pt(II)‐based compounds provide the highest efficiencies, with slight variations upon exchange of the ancillary ligand. In the case of [HLPdCNtBu], both ΦL and τ increase over 30‐fold as compared to RT. Furthermore, the Hg(II) complex achieves, for the first time in its class, a ΦL exceeding 60% and millisecond‐range lifetimes. This demonstrates that a judicious ligand design can pave the way toward versatile coordination compounds with tunable excited state properties. [ABSTRACT FROM AUTHOR]

Rivers are the natural drainage system, transporting anthropogenic wastes and pollution, including microplastics (plastic < 5 mm). In a riverine system, microplastics can enter from different sources, and have spatial variance in concentration, physical and chemical properties, and imposed risk to the ecosystem. This pilot study presents an examination of microplastics in water and sediment samples using a single sample collection from the rural Raquette River, NY to evaluate a hypothesis that distinct locations of the river, such as downstream of a wastewater treatment plant, upstream of a hydro-dam, and river confluence, may be locations of higher microplastics concentration. In general, our results revealed the presence of high microplastic concentrations downstream of the wastewater treatment plant (in sediments), upstream of the hydro dam (both water and sediment), and in the river confluence (water sample), compared to other study sites. Moreover, the risk assessment indicates that even in a rural river with most of its drainage basin comprising forested and agricultural land, water, and sediment samples at all three locations are polluted with microplastics (pollution load index, PLI > 1; PLIzone = 1.87 and 1.68 for water and sediment samples respectively), with risk categories between Levels I and IV ("minor" to "danger"). Overall, the river stands in a "considerable" risk category (PRIzone = 134 and 113 for water and sediment samples respectively). The overall objective of this pilot study was to evaluate our hypothesis and advance our understanding of microplastic dynamics in rural river systems, elucidating their introduction from a point source (wastewater treatment plant), transit through an impediment (hydro-dam), and release into a vital transboundary river (confluence of Raquette-St. Lawrence Rivers). [ABSTRACT FROM AUTHOR]

Two different hybrid nanosystems are prepared by loading highly crystalline, monodisperse magnetite nanocubes (MNCs) with phosphorescent Pt(II) complexes (PtCxs). One involves the encapsulation of the hydrophobic PtCx1 within an amphiphilic comb polymer (MNC@poly(maleic anhydride‐alt‐1‐octadecene) [PMAO]–PtCx1), whereas the other involves the direct binding of the hydrophilic PtCx2 to the surface of the MNC mediated by a ligand‐exchange procedure (MNC@OH–PtCx2). Both systems are evaluated as potential candidates for multimodal imaging in magnetic resonance imaging (MRI) and photoluminescence lifetime imaging micro(spectro)scopy (PLIM). PLIM measurements on agarose phantoms demonstrate significantly longer excited‐state lifetimes compared to the short‐lived autofluorescence of biological background. Additionally, both nanosystems perform as effective MRI contrast agents (CAs): the r2* values are 3–4 times higher than for the commercial CA ferucarbotran. MNC@PMAO–PtCx1 particles also cause significant increases in r2. While the ligand exchange procedure efficiently anchors PtCxs to the MNC surface, the polymeric encapsulation ensures higher colloidal stability, contributing to differences in PLIM and MRI outcomes. In these results, the successful integration of two complementary noninvasive imaging modalities within a single nanosystem is confirmed, serving as the impetus for further investigation of such systems as advanced multimodal–multiscale imaging agents with dual orthogonal readouts. [ABSTRACT FROM AUTHOR]

Perceptual pleasure and its concomitant hedonic value play an essential role in everyday life, motivating behavior and thus influencing how individuals choose to spend their time and resources. However, how pleasure arises from perception of sensory information remains relatively poorly understood. In particular, research has neglected the question of how perceptual representations mediate the relationships between stimulus properties and liking (e.g., stimulus symmetry can only affect liking if it is perceived). The present research addresses this gap for the first time, analyzing perceptual and liking ratings of 96 nonmusicians (power of 0.99) and finding that perceptual representations mediate effects of feature‐based and information‐based stimulus properties on liking for a novel set of melodies varying in balance, contour, symmetry, or complexity. Moreover, variability due to individual differences and stimuli accounts for most of the variance in liking. These results have broad implications for psychological research on sensory valuation, advocating a more explicit account of random variability and the mediating role of perceptual representations of stimulus properties. [ABSTRACT FROM AUTHOR]

Background: Misregistration between CT and PET data can result in mis‐localization and inaccurate quantification of functional uptake in whole body PET/CT imaging. This problem is exacerbated when an abnormal inspiration occurs during the free‐breathing helical CT (FB CT) used for attenuation correction of PET data. In data‐driven gated (DDG) PET, the data selected for reconstruction is typically derived from the end‐expiration (EE) phase of the breathing cycle, making this potential issue worse. Purpose: The objective of this study is to develop a deformable image registration (DIR)‐based respiratory motion model to improve the registration and quantification between misregistered FB CT and PET. Methods: Twenty‐two whole‐body 18F‐FDG PET/CT scans encompassing 48 lesions in misregistered regions were analyzed in this study. End‐inspiration (EI) and EE PET data were derived from −10% to 15% and 30% to 80% of the breathing cycle, respectively. DIR was used to estimate a motion model from the EE to EI phase of the PET data. The model was then used to generate PET images at any phase of up to four times the amplitude of motion between EE and EI for correlation with the misregistered FB CT. Once a matched phase of the FB CT was determined, FB CT was deformed to a pseudo CT at the EE phase (DIR CT). DIR CT was compared with the ground truth DDG CT for AC and localization of the DDG PET. Results: Between DDG PET/FB CT and DDG PET/DIR CT, a significant increase in ∆%SUV was observed (p < 0.01), with median values elevating from 26.7% to 42.4%. This new method was most effective for lesions ≤3 cm proximal to the diaphragm (p < 0.001) but showed decreasing efficacy as the distance increased. When FB CT was severely misregistered with DDG PET (>3 cm), DDG PET/DIR CT outperformed DDG PET/FB CT alone (p < 0.05). Even when patients showed varied breathing patterns during the PET/CT scan, DDG PET/DIR CT still surpassed the efficiency of DDG PET/FB CT (p < 0.01). Though DDG PET/DIR CT couldn't match the performance of the DDG PET/CT ground truth (42.4% vs. 53.6%, p < 0.01), it reached 84% of its quantification, demonstrating good agreement and a strong overall correlation (regression coefficient of 0.94, p < 0.0001). In some cases, anatomical distortion and blurring, and misregistration error were observed in DIR CT, rendering it still unable to correct inaccurate localization near the boundaries of two organs. Conclusions: Based on the motion model derived from gated PET data, DIR CT can significantly improve the quantification and localization of DDG PET. This approach can achieve a performance level of about 84% of the ground truth established by DDG PET/CT. These results show that self‐gated PET and DIR CT may offer an alternative clinical solution to DDG PET and FB CT for quantification without the need for additional cine‐CT imaging. DIR CT was at times inferior to DDG CT due to some distortion and blurring of anatomy and misregistration error. [ABSTRACT FROM AUTHOR]

In electron diffraction, thermal atomic motion produces incoherent scattering over a relatively wide angular range, which appears as a diffuse background that is usually subtracted from measurements of Bragg spot intensities in structure solution methods. The transfer of electron flux from Bragg spots to diffuse scatter is modelled using complex scattering factors f + if′ in the Bloch wave methodology. In a two‐beam Einstein model the imaginary 'absorptive' scattering factor f′ can be obtained by the evaluation of an integral containing f over all possible scattering angles. While more sophisticated models of diffuse scatter are widely used in the electron microscopy community, it is argued in this paper that this simple model is appropriate for current structure solution and refinement methods. The two‐beam model is a straightforward numerical calculation, but even this simplistic approach can become time consuming for simulations of materials with large numbers of atoms in the unit cell and/or many incident beam orientations. Here, a parameterized form of f′ is provided for 103 elements as neutral, spherical atoms that reduces calculation time considerably. [ABSTRACT FROM AUTHOR]

Oral drug absorption kinetics are usually established in populations with a properly functioning gastrointestinal tract. However, many diseases and therapeutics can alter gastrointestinal physiology and cause diarrhea. The extent of diarrhea‐associated impact on drug pharmacokinetics has not been quantitatively described. To address this knowledge gap, we used a population pharmacokinetic modeling approach with data collected in a phase IIa study of matched human immunodeficiency virus (HIV)–infected adults with/without cryptosporidiosis and diarrhea to examine diarrhea‐associated impact on oral clofazimine pharmacokinetics. A population pharmacokinetic model was developed with 428 plasma samples from 23 HIV‐infected adults with/without Cryptosporidium infection using nonlinear mixed‐effects modeling. Covariates describing cryptosporidiosis‐associated diarrhea severity (e.g., number of diarrhea episodes, diarrhea grade) or HIV infection (e.g., viral load, CD4+ T cell count) were evaluated. A two‐compartment model with lag time and first‐order absorption and elimination best fit the data. Maximum diarrhea grade over the study duration was found to be associated with a more than sixfold reduction in clofazimine bioavailability. Apparent clofazimine clearance, intercompartmental clearance, central volume of distribution, and peripheral volume of distribution were 3.71 L/h, 18.2 L/h (interindividual variability [IIV] 45.0%), 473 L (IIV 3.46%), and 3434 L, respectively. The absorption rate constant was 0.625 h−1 (IIV 149%) and absorption lag time was 1.83 h. In conclusion, the maximum diarrhea grade observed for the duration of oral clofazimine administration was associated with a significant reduction in clofazimine bioavailability. Our results highlight the importance of studying disease impacts on oral therapeutic pharmacokinetics to inform dose optimization and maximize the chance of treatment success. [ABSTRACT FROM AUTHOR]

Forests contain substantial carbon stores, including above and belowground biomass and living and non-living biomass. Different management regimes produce different outcomes related to stored and sequestered carbon in forests. The geographic focus of this study is the Wabanaki-Acadian Forest of the Maritime Provinces of Canada (New Brunswick, Nova Scotia, and Prince Edward Island). This study reviews the literature to evaluate the carbon impacts of (1) intensive forest management for fiber products, (2) unharvested (or conservation) forest, and (3) climate-focused, ecological forestry. Each of these forest management strategies and concomitant silviculture regimes sequester and store carbon at varying rates and across different carbon pools in the forest. The literature suggests that unharvested (conservation) forests store and sequester the most carbon, and traditional, intensive fiber management stores and sequesters the least. Ecological forestry may provide the best balance between carbon sequestration and storage and climate adaptability, while also allowing for the provision of some timber/fiber products. This study also discusses the co-benefits offered by forests under each of the three management regimes. New research, in general and in the region, needs to examine further belowground carbon dynamics in soil as most efforts to document carbon focus on aboveground carbon pools. [ABSTRACT FROM AUTHOR]

Deep gluteal syndrome is a clinical condition in which discomfort may arise due to the pathoanatomy of the subgluteal space. We conducted an anatomical exploration to categorize the relationship of the piriformis muscle, sciatic nerve (SN), and pudendal nerve (PN) to the ischial spine (IS) and sacrospinous ligament. We analyzed 22 cadavers. The piriformis muscle, SN, and PN were exposed through either a transgluteal approach or a gluteal flap. The relationship of the neural structures to the IS, sacrospinous ligament, and ischial bone as they exit the greater sciatic foramen was observed, and the exit zones were classified as zone A, medial to the IS (entirely on sacrospinous ligament); zone B, on the IS; and zone C, lateral to the IS (entirely on ischial bone). The SN was observed either in zone B or zone C in all specimens. The PN was found to be in either zone A or zone B in 97.6% of specimens. The most common combinations were SN in zone B and PN in zone A (type I), and SN in zone C and PN in zone B (type II). The results from this study show clear anatomical differences in the SN-PN relationship, which may play a role in pain seen in deep gluteal syndrome. Moreover, classification of the SN-IS and PN-IS relationships described in this article will help describe different pathologies affecting the deep gluteal area. [ABSTRACT FROM AUTHOR]

Anomia, or difficulty naming common objects, is the most common, acquired impairment of language. Effective therapeutic interventions for anomia typically involve massed practice at high doses. This requires significant investment from patients and therapists. Aphasia researchers have increasingly looked to neurostimulation to accelerate these treatment effects, but the evidence behind this intervention is sparse and inconsistent. Here, we hypothesised that group-level neurostimulation effects might belie a more systematic structure at the individual level. We sought to test the hypothesis by attempting to predict the immediate (online), individual-level behavioural effects of anodal and sham neurostimulation in 36 chronic patients with anomia, performing naming and size judgement tasks. Using clinical, (pre-stimulation) behavioural and MRI data, as well as Partial Least Squares regression, we attempted to predict neurostimulation effects on accuracies and reaction times of both tasks. Model performance was assessed via cross-validation. Predictive performances were compared to that of a null model, which predicted the mean neurostimulation effects for all patients. Models derived from pre-stimulation data consistently outperformed the null model when predicting neurostimulation effects on both tasks' performance. Notably, we could predict behavioural declines just as well as improvements. In conclusion, inter-patient variation in online responses to neurostimulation is, to some extent, systematic and predictable. Since declines in performance were just as predictable as improvements, the behavioural effects of neurostimulation in patients with anomia are unlikely to be driven by placebo effects. However, the online effect of the intervention appears to be as likely to interfere with task performance as to improve it. [ABSTRACT FROM AUTHOR]

This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident. Consequently, exciting applications in small molecule activation have been developed, including in catalytic transformations. This article intends to guide the reader through the fascinating world of low-valent transition metalates. The first part of the review describes the synthesis and reactivity of d-block metalates stabilized by an assortment of ligand frameworks, including carbonyls, isocyanides, alkenes and polyarenes, phosphines and phosphorus heterocycles, amides, and redox-active nitrogen-based ligands. Thereby, the reader will be familiarized with the impact of different ligand types on the physical and chemical properties of metalates. In addition, ion-pairing interactions and metal–metal bonding may have a dramatic influence on metalate structures and reactivities. The complex ramifications of these effects are examined in a separate section. The second part of the review is devoted to the reactivity of the metalates toward small inorganic molecules such as H2, N2, CO, CO2, P4 and related species. It is shown that the use of highly electron-rich and reactive metalates in small molecule activation translates into impressive catalytic properties in the hydrogenation of organic molecules and the reduction of N2, CO, and CO2. The results discussed in this review illustrate that the potential of transition metalate anions is increasingly being tapped for challenging catalytic processes with relevance to organic synthesis and energy conversion. Therefore, it is hoped that this review will serve as a useful resource to inspire further developments in this dynamic research field. [ABSTRACT FROM AUTHOR]

Despite the accessibility of numerous transition metal polyphosphido complexes through transition‐metal‐mediated activation of white phosphorus, the targeted functionalization of Pn ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo‐P4 ligands, leading to the discovery of acylcyanophosphanides and ‐phosphines. Treatment of the complex [K(18c‐6)][(Ar*BIAN)Co(η4‐P4)] ([K(18c‐6)]3, 18c‐6=[18]crown‐6, Ar*=2,6‐dibenzhydryl‐4‐isopropylphenyl, BIAN=1,2‐bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η4‐P4C(O)R)] (R=tBu, Cy, 1‐Ad, Ph; 4 a–d). Subsequent reactions of 4 a–d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN]− (9 a–d−) and the cyclo‐P3 cobaltate anion [(Ar*BIAN)Co(η3‐P3)(CN)]− (8−). Further reactions of 4 a–d with trimethylsilyl cyanide (Me3SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P4C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c‐6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O))2PCN (10). [ABSTRACT FROM AUTHOR]

Despite the accessibility of numerous transition metal polyphosphido complexes through transition‐metal‐mediated activation of white phosphorus, the targeted functionalization of Pn ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo‐P4 ligands, leading to the discovery of acylcyanophosphanides and ‐phosphines. Treatment of the complex [K(18c‐6)][(Ar*BIAN)Co(η4‐P4)] ([K(18c‐6)]3, 18c‐6=[18]crown‐6, Ar*=2,6‐dibenzhydryl‐4‐isopropylphenyl, BIAN=1,2‐bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η4‐P4C(O)R)] (R=tBu, Cy, 1‐Ad, Ph; 4 a–d). Subsequent reactions of 4 a–d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN]− (9 a–d−) and the cyclo‐P3 cobaltate anion [(Ar*BIAN)Co(η3‐P3)(CN)]− (8−). Further reactions of 4 a–d with trimethylsilyl cyanide (Me3SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P4C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c‐6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O))2PCN (10). [ABSTRACT FROM AUTHOR]

• New caenagnathid specimens are described from the Late Cretaceous of West Texas. • Most complete caenagnathids known from the southern Western Interior. • Adds new comparative material representing the scant 'southern' caenagnathid record. • Osteohistology and phylogeny helps resolve caeanagnathid dinosaur affinities. • The work represents a vital 'southern' dinosaur paleofaunal datum for North America. New caenagnathid dinosaur specimens from the upper Aguja Formation of West Texas comprise the most complete examples yet described from southern North America. Two individuals are represented. Osteohistology indicates that both were mature at their times of death. Although they share no overlapping elements, the two individuals are separated by overall body size, paleohabitat, and stratigraphic position and so they almost certainly represent different species. One individual consists of a partial hindlimb, but exhibits too few (3) characters to be phylogenetically informative and is, therefore, referred to an indeterminate caenagnathid – possibly one of two species previously recognized in coastal facies of the Aguja Formation. The second individual is more complete. It was recovered higher in section from more inland fluvial paleoenvironments and preserves fragmentary elements from throughout the postcranial skeleton. A histology-based growth model – the first for a caenagnathid – indicates that the second individual required at least five years to approach fully adult size. However, only 11 character states could be derived from its preserved remains. Phylogenetic analyses found this specimen deeply nested within Caenagnathidae, but were otherwise inconclusive and so it, too, is referred to an indeterminate caenagnathid. Nevertheless, several combined morphologies (e.g., absence of cervical epipophyses, dorsoventral depth of the hypapophysis on the second cervicodorsal vertebra, and greater trochanter of the femur only weakly separated from the femoral head) implies that the second individual represents an unknown species. One critical aspect of both specimens is that they provide significant new comparative material representing the sparse 'southern' caenagnathid record. [ABSTRACT FROM AUTHOR]

Objectives Preparing for old age is an adaptive behavior with positive consequences on well-being. This study examined; (a) the degree to which the importance associated with positive outcomes within specific domains of everyday functioning (e.g. social relationships, health) varies across ages and cultures; (b) the impact of importance on preparing for old age; and (c) whether the effects of importance were greater in later life. Methods Using data from adults aged 30–85 years in Germany (n = 623), Hong Kong (n = 317), and the United States (n = 313) collected over 5 years, we examined variations in importance ratings across age, cultures, and behavioral domains, and the extent to which age and importance predicted preparations. Results Importance ratings were found to vary with age, time of test, domains, and culture, reflecting the expected contextual effects. Importance also was a positive predictor of preparations, with the strength of prediction being somewhat greater in old age. Discussion The results provide evidence that the perceived importance of functioning within domains is affected by a number of contextual factors, including the domain of everyday function and culture. Given that importance also predicts preparations, such variation may help explain differences in preparations across contexts. In line with selective engagement theory, some support was also obtained for the prediction that older adults are more selective in engaging resources in support of preparations. Such selectivity can be viewed as an adaptive response to diminishing personal resources in later life. [ABSTRACT FROM AUTHOR]