Plutonium oxide melt structure and covalency.

Advances in nuclear power reactors include the use of mixed oxide fuel, containing uranium and plutonium oxides. The high-temperature behaviour and structure of PuO2-x above 1,800 K remain largely unexplored, and these conditions must be considered for reactor design and planning for the mitigation of severe accidents. Here, we measure the atomic structure of PuO2-x through the melting transition up to 3,000 ± 50 K using X-ray scattering of aerodynamically levitated and laser-beam-heated samples, with O/Pu ranging from 1.57 to 1.76. Liquid structural models consistent with the X-ray data are developed using machine-learned interatomic potentials and density functional theory. Molten PuO1.76 contains some degree of covalent Pu-O bonding, signalled by the degeneracy of Pu 5f and O 2p orbitals. The liquid is isomorphous with molten CeO1.75, demonstrating the latter as a non-radioactive, non-toxic, structural surrogate when differences in the oxidation potentials of Pu and Ce are accounted for. These characterizations provide essential constraints for modelling pertinent to reactor safety design.

Modeling the Structure of Ketoprofen-Poly(vinylpyrrolidone) Amorphous Solid Dispersions with Empirical Potential Structure Refinements of X-ray Scattering Data.

The metastability of amorphous formulations poses barriers to their safe and widespread commercialization. The propensity of amorphous solid dispersions (ASDs) to crystallize is directly linked to their molecular structure. Amorphous structures are inherently complex and thus difficult to fully characterize by experiments, which makes structural simulations an attractive route for investigating which structural characteristics correlate with ASD stability. In this study, we use empirical potential structure refinement (EPSR) to create molecular models of ketoprofen-poly(vinylpyrrolidone) (KTP/PVP) ASDs with 0-75 wt % drug loading. The EPSR technique uses X-ray total scattering measurements as constraints, yielding models that are consistent with the X-ray data. We perform several simulations to assess the sensitivity of the EPSR approach to input parameters such as intramolecular bond rotations, PVP molecule length, and PVP tacticity. Even at low drug loading (25 wt %), ∼40% of KTP molecules participate in KTP-KTP hydrogen bonding. The extent of KTP-PVP hydrogen bonding does not decrease significantly at higher drug loadings. However, the models' relative uncertainties are too large to conclude whether ASDs' lower stabilities at high drug loadings are due to changes in drug-excipient hydrogen bonding or a decrease in steric hindrance of KTP molecules. This study illustrates how EPSR, combined with total scattering measurements, can be a powerful tool for investigating structural characteristics in amorphous formulations and developing ASDs with improved stability.

Current and Future Effects of Climate Change on Airborne Allergens.

PURPOSE OF REVIEW: Delineation of the impact of elevated carbon dioxide and concomitant global warming on airborne allergens is performed. RECENT FINDINGS: European tree pollen trends in general showed earlier start and end dates and increased total pollen release, with some differences both in locale and among species. Earlier flowering was also seen with grasses and weeds. In the case of some boreal trees, flowering was delayed due to a pre-seasonal requirement for necessary accumulated chilling temperature to achieve bud-set. Anthropogenic climate change induced rise in temperature and CO2 levels has resulted in demonstrable increases in aeroallergens. This has been most dramatic in tree pollen annual load, but also seen with grasses and weeds. Collected data is greatest for the Northern Hemisphere, especially the European continent, with supporting data from North America and Australia.

Assessing cross-reactivity in allergen immunotherapy.

Knowledge of patterns of pollen cross-reactivity is crucial for formulation of immunotherapy vaccines. As phylogenetic relationships have become better clarified through the use of tools such as gene sequencing, it is apparent that cross-reactivity reflects taxonomy in the vast majority of cases. Contradictory observations of unexpected cross-reactivity between distantly related plants require explanation. There are many proteins, presumably performing vital functions, tightly preserved throughout the evolutionary tree from plants to animals. Examples are profilins, lipid transfer proteins, and pathogenesis-related proteins. These may function as panallergens. The small differences that exist between these ubiquitous proteins may explain why these are frequently minor allergens, not reacting in the majority of allergic sera. This article summarizes cross-reactivity from older studies using crude pollen extracts as well as newer research of purified or recombinant allergenic proteins. The patterns of cross-allergenicity that emerge should be helpful in guiding therapeutic decisions.

Predicting student performance using sequence classification with time-based windows.

A growing number of universities worldwide use various forms of online and blended learning as part of their academic curricula. Furthermore, the recent changes caused by the COVID-19 pandemic have led to a drastic increase in importance and ubiquity of online education. Among the major advantages of e-learning is not only improving students' learning experience and widening their educational prospects, but also an opportunity to gain insights into students' learning processes with learning analytics. This study contributes to the topic of improving and understanding e-learning processes in the following ways. First, we demonstrate that accurate predictive models can be built based on sequential patterns derived from students' behavioral data, which are able to identify underperforming students early in the course. Second, we investigate the specificity-generalizability trade-off in building such predictive models by investigating whether predictive models should be built for every course individually based on course-specific sequential patterns, or across several courses based on more general behavioral patterns. Finally, we present a methodology for capturing temporal aspects in behavioral data and analyze its influence on the predictive performance of the models. The results of our improved sequence classification technique are capable to predict student performance with high levels of accuracy, reaching 90% for course-specific models.

Allergy to oak pollen in North America.

Background: Oak pollen is an important allergen in North America. The genus Quercus (oak) belongs to the family Fagaceae under the order Fagales. Objective: The objective of this article was to narratively review the oak pollen season, clinical and epidemiologic aspects of allergy to oak pollen, oak taxonomy, and oak allergen cross-reactivity, with a focus on the North American perspective. Methods: A PubMed literature review (no limits) was conducted. Publications related to oak pollen, oak-related allergic rhinitis with or without conjunctivitis, and oak-related allergic asthma were selected for review. Results: Oak species are common throughout the United States and contribute up to 50% to overall atmospheric pollen loads. Mean peak oak pollen counts can reach >2000 grains/m³. The start of the oak pollen season generally corresponds to the seasonal shift from winter to spring based on latitude and elevation, and may begin as early as mid February. The duration of the season can last > 100 days and, in general, is longer at lower latitudes. In the United States, ∼30% of individuals with allergy are sensitized to oak. The oak pollen season correlates with increased allergic rhinitis symptom-relieving medication use and asthma-related emergency department visits or hospitalizations. Oak falls within the birch homologous group. Extensive immunologic cross-reactivity has been demonstrated between oak pollen and birch pollen allergens, and, more specifically, their major allergens Que a 1 and Bet v 1. The cross-reactivity between oak and birch has implications for allergy immunotherapy (AIT) because guidelines suggest selecting one representative allergen within a homologous group for AIT, a principle that would apply to oak. Conclusion: Allergy to oak pollen is common in North America and has a substantial clinical impact. Oak pollen allergens are cross-reactive with birch pollen allergens, which may have implications for AIT.

In Situ High-Temperature Synchrotron Diffraction Studies of (Fe,Cr,Al)3O4 Spinels.

The modeling of a loss-of-coolant-accident scenario involving nuclear fuels with FeCrAl cladding materials in consideration to replace a Zircaloy requires knowledge of the thermodynamics of oxidized structures. At temperatures higher than 1500 °C, oxidation of FeCrAl alloys forms (Fe,Cr,Al)3O4 spinels. In situ high-energy X-ray diffraction in a conical nozzle levitator installed at beamline 6-ID-D of the APS was used to study the structural evolution of the oxides as a function of the temperature. Single-phase (spinel) and multiphase (spinel-corundum-FeAlO3) regions are mapped as a function of the temperature for three different compositions of FeCrAl oxidation products. The thermal expansion coefficients and cation distribution in the spinel structure have been refined. The temperature at which complete melting of the fuel cladding is expected has been determined by the liquidus temperatures of the oxidized products to be between 1657 and 1834 °C in a 20% O2/Ar atmosphere using the cooling trace method. The liquidus temperature increases with increasing Al and Cr content in the spinel phase.

The impact of weather and climate on pollen concentrations in Denver, Colorado, 2010-2018.

BACKGROUND: Increasing evidence indicates that climate change is affecting the timing of pollen season and concentrations of allergenic pollens. To date, pollen trends and their associations with meteorological variables have not been studied in most of the United States. OBJECTIVE: The purpose of this study was to investigate the effects of weather and climate on pollen concentrations and pollen season timing in Denver, Colorado. METHODS: We retrospectively analyzed tree, grass, and weed pollen counts and meteorological variables from 2010-2018 using linear and Poisson regression models. RESULTS: Pollen season timing did not demonstrate uniform trends from 2010 to 2018. Certain species demonstrated earlier season start dates (linden, oak) or end dates (birch, maple), and others had later end dates (oak, grass). Only a few species demonstrated changes in season duration (linden, oak, maple, birch) and peak date (maple, birch). Pollen concentrations either remained stable or increased over the years. Temperature and carbon dioxide levels increased over the study period, with the exception of decreased temperature in August. Wind speed remained stable or decreased over the study period. CONCLUSION: This study illustrates the complex interactions between pollens and meteorology. Meteorological variables associated with climate change do appear to affect allergenic pollens, though the relationship is variable both amongst pollens and from year to year.

Short ragweeds is highly cross-reactive with other ragweeds.

BACKGROUND: The most widespread ragweed (Ambrosia) species in North America are short ragweed (Ambrosia artemisiifolia; Amb a), giant ragweed (Ambrosia trifida; Amb t), and western ragweed (Ambrosia psilostachya; Amb p). Varied geographic distributions of ragweed species raise questions regarding the need for ragweed species-specific allergen immunotherapy. OBJECTIVE: To determine allergenic cross-reactivity among ragweed species by immunologic analyses of sera from subjects allergic to ragweed from North America and Europe. METHODS: Sera were collected from 452 subjects allergic to ragweed who participated in Amb a sublingual immunotherapy tablet clinical trials. All subjects had positive skin prick test and serum IgE against Amb a. Ragweed-specific IgE (pre treatment) and IgG4 (post treatment) were measured by ImmunoCAP. IgE inhibition studies among Amb a, Amb t, and Amb p were conducted. Using pooled sera from another ragweed-allergic population, IgE inhibition studies of 7 less widespread Ambrosia species also were conducted. RESULTS: A strong correlation between Amb a vs Amb p and Amb t serum IgE levels was observed. In the vast majority of pretreatment sera, Amb a inhibited Amb a, Amb p, and Amb t IgE reactivity by more than 90%. Strong correlations were observed between Amb a vs Amb p and Amb t post-treatment IgG4 levels. In pooled sera, Amb a extract inhibited the binding of serum IgE to all 10 ragweed species by 98%-100%. CONCLUSION: In a population of subjects allergic to Amb a, substantial allergenic cross-reactivity among Amb a, Amb p, and Amb t was demonstrated. These in vitro data suggest that an Amb a-based single-species ragweed allergen immunotherapy may be therapeutically active in patients exposed to diverse ragweed pollens. TRIAL REGISTRY: Clinicaltrials.gov, NCT00770315, NCT00783198, and NCT00330083.

Molecular structure of ketoprofen-polyvinylpyrrolidone solid dispersions prepared by different amorphization methods.

Amorphous solid dispersions (ASDs) are a widely studied formulation approach for improving the bioavailability of poorly water-soluble pharmaceuticals. Yet, a complete understanding remains lacking for how specific processing methods may influence ASDs' molecular structure. We prepare ketoprofen/polyvinylpyrrolidone (KTP/PVP) ASDs, ranging from 0-75 wt% KTP, using five different amorphization techniques: melt quenching, rotary evaporation with vacuum drying, spray drying, and acoustic levitation with either a premixed solution or in situ mixing of separate co-sprayed solutions. The co-spray levitation approach enables on-demand compositional changes in a containerless processing environment, while requiring minimal pharmaceutical material (∼1 mg). The structure of all ASDs are then compared using high-energy X-ray total scattering. X-ray pair distribution functions are similar for most ASDs of a given composition (Rx = 0.4-2.5%), which is consistent with them having similar intramolecular structure. More notably, differences in the X-ray structure factors for the various amorphization routes indicate differing extents of molecular mixing, a direct indication of their relative stability against crystallization. Melt quenching, spray drying, and levitation of premixed solutions exhibit some degree of molecular mixing, while the co-sprayed levitation samples have molecular arrangements like those of KTP/PVP physical mixtures. These findings illustrate how X-ray total scattering can be used to benchmark amorphous forms prepared by different techniques.

Microgravity effects on nonequilibrium melt processing of neodymium titanate: thermophysical properties, atomic structure, glass formation and crystallization.

The relationships between materials processing and structure can vary between terrestrial and reduced gravity environments. As one case study, we compare the nonequilibrium melt processing of a rare-earth titanate, nominally 83TiO2-17Nd2O3, and the structure of its glassy and crystalline products. Density and thermal expansion for the liquid, supercooled liquid, and glass are measured over 300-1850 °C using the Electrostatic Levitation Furnace (ELF) in microgravity, and two replicate density measurements were reproducible to within 0.4%. Cooling rates in ELF are 40-110 °C s-1 lower than those in a terrestrial aerodynamic levitator due to the absence of forced convection. X-ray/neutron total scattering and Raman spectroscopy indicate that glasses processed on Earth and in microgravity exhibit similar atomic structures, with only subtle differences that are consistent with compositional variations of ~2 mol. % Nd2O3. The glass atomic network contains a mixture of corner- and edge-sharing Ti-O polyhedra, and the fraction of edge-sharing arrangements decreases with increasing Nd2O3 content. X-ray tomography and electron microscopy of crystalline products reveal substantial differences in microstructure, grain size, and crystalline phases, which arise from differences in the melt processes.

First blood: An efficient, hybrid one- and zero-dimensional, modular hemodynamic solver.

Low-dimensional (1D or 0D) models can describe the whole human blood circulation, for example, 1D distributed parameter model for the arterial network and 0D concentrated models for the heart or other organs. This paper presents a combined 1D-0D solver, called first_blood, that solves the governing equations of fluid dynamics to model low-dimensional hemodynamic effects. An extended method of characteristics is applied here to solve the momentum, and mass conservation equations and the viscoelastic wall model equation, mimicking the material properties of arterial walls. The heart and the peripheral lumped models are solved with a general zero-dimensional (0D) nonlinear solver. The model topology can be modular, that is, first_blood can solve any 1D-0D hemodynamic model. To demonstrate the applicability of first_blood, the human arterial system, the heart and the peripherals are modelled using the solver. The simulation time of a heartbeat takes around 2 s, that is, first_blood requires only twice the real-time for the simulation using an average PC, which highlights the computational efficiency. The source code is available on GitHub, that is, it is open source. The model parameters are based on the literature suggestions and on the validation of output data to obtain physiologically relevant results.

A hyperbaric aerodynamic levitator for containerless materials research.

A hyperbaric aerodynamic levitator has been developed for containerless materials research at specimen temperatures exceeding 2000 °C and pressures up to 10.3 MPa (1500 psi). This report describes the prototype instrument design and observations of the influence of specimen size, density, pressure, and flow rate on levitation behavior. The effect of pressure on heat transfer was also assessed by studying the heating and cooling behavior of levitated Al2O3 liquids. A threefold increase in the convective heat transfer coefficient was estimated as pressure increased to 10.3 MPa. The results demonstrate that hyperbaric aerodynamic levitation is a promising technique for containerless materials research at high gas pressures.

Acoustic levitation: recent developments and emerging opportunities in biomaterials research.

Containerless sample environments (levitation) are useful for study of nucleation, supercooling, and vitrification and for synthesis of new materials, often with non-equilibrium structures. Elimination of extrinsic nucleation by container walls extends access to supercooled and supersaturated liquids under high-purity conditions. Acoustic levitation is well suited to the study of liquids including aqueous solutions, organics, soft materials, polymers, and pharmaceuticals at around room temperature. This article briefly reviews recent developments and applications of acoustic levitation in materials R&D. Examples of experiments yielding amorphous pharmaceutical materials are presented. The implementation and results of experiments on supercooled and supersaturated liquids using an acoustic levitator at a high-energy X-ray beamline are described.

Octahedral oxide glass network in ambient pressure neodymium titanate.

Rare-earth titanates form very fragile liquids that can be made into glasses with useful optical properties. We investigate the atomic structure of 83TiO2-17Nd2O3 glass using pair distribution function (PDF) analysis of X-ray and neutron diffraction with double isotope substitutions for both Ti and Nd. Six total structure factors are analyzed (5 neutron + 1 X-ray) to obtain complementary sensitivities to O and Ti/Nd scattering, and an empirical potential structure refinement (EPSR) provides a structural model consistent with the experimental measurements. Glass density is estimated as 4.72(13) g cm-3, consistent with direct measurements. The EPSR model indicates nearest neighbor interactions for Ti-O at [Formula: see text] = 1.984(11) Å with coordination of [Formula: see text] = 5.72(6) and for Nd-O at [Formula: see text] = 2.598(22) Å with coordination of [Formula: see text] = 7.70(26), in reasonable agreement with neutron first order difference functions for Ti and Nd. The titanate glass network comprises a mixture of distorted Ti-O5 and Ti-O6 polyhedra connected via 71% corner-sharing and 23% edge-sharing. The O-Ti coordination environments include 15% nonbridging O-Ti1, 51% bridging O-Ti2, and 32% tricluster O-Ti3. This structure is highly unusual for oxide glasses melt-quenched at ambient pressure, as it consists of Ti-Ox predominantly in octahedral (with nearly no tetrahedral) coordination.

Phase separation in mullite-composition glass.

Aluminosilicates (AS) are ubiquitous in ceramics, geology, and planetary science, and their glassy forms underpin vital technologies used in displays, waveguides, and lasers. In spite of this, the nonequilibrium behavior of the prototypical AS compound, mullite (40SiO2-60Al2O3, or AS60), is not well understood. By deeply supercooling mullite-composition liquid via aerodynamic levitation, we observe metastable liquid-liquid unmixing that yields a transparent two-phase glass, comprising a nanoscale mixture of AS7 and AS62. Extrapolations from X-ray scattering measurements show the AS7 phase is similar to vitreous SiO2 with a few Al species substituted for Si. The AS62 phase is built from a highly polymerized network of 4-, 5-, and 6-coordinated AlOx polyhedra. Polymerization of the AS62 network and the composite morphology provide essential mechanisms for toughening the glass.

The Structure of Liquid and Glassy Carbamazepine.

To enhance the solubility of orally administered pharmaceuticals, liquid capsules or amorphous tablets are often preferred over crystalline drug products. However, little is known regarding the variation in bonding mechanisms between pharmaceutical molecules in their different disordered forms. In this study, liquid and melt-quenched glassy carbamazepine have been studied using high energy X-ray diffraction and modeled using Empirical Potential Structure Refinement. The results show significant structural differences between the liquid and glassy states. The liquid shows a wide range of structures; from isolated molecules, to aromatic ring correlations and NH-O hydrogen bonding. Upon quenching from the liquid to the glass the number of hydrogen bonds per molecule increases by ~50% at the expense of a ~30% decrease in the close contact (non-bonded) carbon-carbon interactions between aromatic rings. During the cooling process, there is an increase in both singly and doubly hydrogen-bonded adjacent molecules. Although hydrogen-bonded dimers found in the crystalline states persist in the glassy state, the absence of a crystalline lattice also allows small, hydrogen-bonded NH-O trimers and tetramers to form. This proposed model for the structure of glassy carbamazepine is consistent with the results from vibrational spectroscopy and nuclear magnetic resonance.

Novel Method to Detect Pitfalls of Intracoronary Pressure Measurements by Pressure Waveform Analysis.

Potential pitfalls of fractional flow reserve (FFR) measurements are well-known drawbacks of invasive physiology measurement, e.g., significant drift of the distal pressure trace may lead to the misclassification of stenoses. Thus, a simultaneous waveform analysis of the pressure traces may be of help in the quality control of these measurements by online detection of such artefacts as the drift or the wedging of the catheter. In the current study, we analysed the intracoronary pressure waveform with a dedicated program. In 130 patients, 232 FFR measurements were performed and derivative pressure curves were calculated. Local amplitude around the dicrotic notch was calculated from the distal intracoronary pressure traces (δdPn/dt). A unidimensional arterial network model of blood flow was employed to simulate the intracoronary pressure traces at different flow rates. There was a strong correlation between δdPn/dt values measured during hyperaemia and FFR (r = 0.88). Diagnostic performance of distal δdPn/dt ≤ 3.52 for the prediction of FFR ≤ 0.80 was 91%. The correlation between the pressure gradient and the corresponding δdPn/dt values obtained from all measurements independently of the physiological phase was also significant (r = 0.80). During simulation, the effect of flow rate on δdPn/dt further supported the close correlation between the pressure ratios and δdPn/dt. Discordance between the FFR and the δdPn/dt can be used as an indicator of possible technical problems of FFR measurements. Hence, an online calculation of the δdPn/dt may be helpful in avoiding some pitfalls of FFR evaluation.

Increasing the capacity of water distribution networks using fitness function transformation.

Even the most carefully designed water distribution network (WDN) can suffer from local capacity deficiencies as a result of the quick and unpredictable growth of the urbanization of new industrial sites. To solve this problem, this paper focuses on the identification of the best possible location for a new pipeline within an existing WDN, which maximizes the node-wise capacity. To determine the optimal solution, a parameter, namely pressure sensitivity, is defined, which can localize nodes with local capacity problems computationally efficiently. During our research, a fitness function transformation technique was defined, which increases the effectivity of the optimization on a larger scale by the formulation of a feasible fitness function. Combining this technique with an extended version of the genetic algorithm, the topology of eleven real-life WDN was optimized. A scrutiny is performed on three networks, highlighting typical deficiencies.