Direct Visualization of Chemical Transport in Solid-State Chemical Reactions by Time-of-Flight Secondary Ion Mass Spectrometry.

Systematic control and design of solid-state chemical reactions are required for modifying materials properties and in novel synthesis. Understanding chemical dynamics at the nanoscale is therefore essential to revealing the key reactive pathways. Herein, we combine focused ion beam-scanning electron microscopy (FIB-SEM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) to track the migration of sodium from a borate coating to the oxide scale during in situ hot corrosion testing. We map the changing distribution of chemical elements and compounds from 50 to 850 °C to reveal how sodium diffusion induces corrosion. The results are validated by in situ X-ray diffraction and post-mortem TOF-SIMS. We additionally retrieve the through-solid sodium diffusion rate by fitting measurements to a Fickian diffusion model. This study presents a step change in analyzing microscopic diffusion mechanics with high chemical sensitivity and selectivity, a widespread analytical challenge that underpins the defining rates and mechanisms of solid-state reactions.

Effective Suppressing Phase Segregation of Mixed-Halide Perovskite by Glassy Metal-Organic Frameworks.

Lead mixed-halide perovskites offer tunable bandgaps for optoelectronic applications, but illumination-induced phase segregation can quickly lead to changes in their crystal structure, bandgaps, and optoelectronic properties, especially for the Br-I mixed system because CsPbI3 tends to form a non-perovskite phase under ambient conditions. These behaviors can impact their performance in practical applications. By embedding such mixed-halide perovskites in a glassy metal-organic framework, a family of stable nanocomposites with tunable emission is created. Combining cathodoluminescence with elemental mapping under a transmission electron microscope, this research identifies a direct relationship between the halide composition and emission energy at the nanoscale. The composite effectively inhibits halide ion migration, and consequently, phase segregation even under high-energy illumination. The detailed mechanism, studied using a combination of spectroscopic characterizations and theoretical modeling, shows that the interfacial binding, instead of the nanoconfinement effect, is the main contributor to the inhibition of phase segregation. These findings pave the way to suppress the phase segregation in mixed-halide perovskites toward stable and high-performance optoelectronics.

Propranolol Reduces p-tau Accumulation and Improves Behavior Outcomes in a Polytrauma Murine Model.

INTRODUCTION: Traumatic brain injury (TBI) can lead to neurocognitive decline, in part due to phosphorylated tau (p-tau). Whether p-tau accumulation worsens in the setting of polytrauma remains unknown. Propranolol has shown clinical benefit in head injuries; however, the underlying mechanism is also unknown. We hypothesize that hemorrhagic shock would worsen p-tau accumulation but that propranolol would improve functional outcomes on behavioral studies. METHODS: A murine polytrauma model was developed to examine the accumulation of p-tau and whether it can be mitigated by early administration of propranolol. TBI was induced using a weight-drop model and hemorrhagic shock was achieved via controlled hemorrhage for 1 h. Mice were given intraperitoneal propranolol 4 mg/kg or saline control. The animals underwent behavioral testing at 30 d postinjury and were sacrificed for cerebral histological analysis. These studies were completed in male and female mice. RESULTS: TBI alone led to increased p-tau generation compared to sham on both immunohistochemistry and immunofluorescence (P < 0.05). The addition of hemorrhage led to greater accumulation of p-tau in the hippocampus (P < 0.007). In male mice, p-tau accumulation decreased with propranolol administration for both polytrauma and TBI alone (P < 0.0001). Male mice treated with propranolol also outperformed saline-control mice on the hippocampal-dependent behavioral assessment (P = 0.0013). These results were not replicated in female mice; the addition of hemorrhage did not increase p-tau accumulation and propranolol did not demonstrate a therapeutic effect. CONCLUSIONS: Polytrauma including TBI generates high levels of hippocampal p-tau, but propranolol may help prevent this accumulation to improve both neuropathological and functional outcomes in males.

Automated Image Analysis for Single-Atom Detection in Catalytic Materials by Transmission Electron Microscopy.

Single-atom catalytic sites may have existed in all supported transition metal catalysts since their first application. Yet, interest in the design of single-atom heterogeneous catalysts (SACs) only really grew when advances in transmission electron microscopy (TEM) permitted direct confirmation of metal site isolation. While atomic-resolution imaging remains a central characterization tool, poor statistical significance, reproducibility, and interoperability limit its scope for deriving robust characteristics about these frontier catalytic materials. Here, we introduce a customized deep-learning method for automated atom detection in image analysis, a rate-limiting step toward high-throughput TEM. Platinum atoms stabilized on a functionalized carbon support with a challenging irregular three-dimensional morphology serve as a practically relevant test system with promising scope in thermo- and electrochemical applications. The model detects over 20,000 atomic positions for the statistical analysis of important properties for establishing structure-performance relations over nanostructured catalysts, like the surface density, proximity, clustering extent, and dispersion uniformity of supported metal species. Good performance obtained on direct application of the model to an iron SAC based on carbon nitride demonstrates its generalizability for single-atom detection on carbon-related materials. The approach establishes a route to integrate artificial intelligence into routine TEM workflows. It accelerates image processing times by orders of magnitude and reduces human bias by providing an uncertainty analysis that is not readily quantifiable in manual atom identification, improving standardization and scalability.

Elucidation of Metal Local Environments in Single-Atom Catalysts Based on Carbon Nitrides.

The ability to tailor the properties of metal centers in single-atom heterogeneous catalysts depends on the availability of advanced approaches for characterization of their structure. Except for specific host materials with well-defined metal adsorption sites, determining the local atomic environment remains a crucial challenge, often relying heavily on simulations. This article reports an advanced analysis of platinum atoms stabilized on poly(triazine imide), a nanocrystalline form of carbon nitride. The approach discriminates the distribution of surface coordination sites in the host, the evolution of metal coordination at different stages during the synthesis of the material, and the potential locations of metal atoms within the lattice. Consistent with density functional theory predictions, simultaneous high-resolution imaging in high-angle annular dark field and bright field modes experimentally confirms the preferred localization of platinum in-plane in the corners of the triangular cavities. X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and dynamic nuclear polarization enhanced 15 N nuclear magnetic resonance (DNP-NMR) spectroscopies coupled with density functional theory (DFT) simulations reveal that the predominant metal species comprise Pt(II) bound to three nitrogen atoms and one chlorine atom inside the coordination sites. The findings, which narrow the gap between experimental and theoretical elucidation, contribute to the improved structural understanding and provide a benchmark for exploring the speciation of single-atom catalysts based on carbon nitrides.

Nanomagnetic properties of the meteorite cloudy zone.

Meteorites contain a record of their thermal and magnetic history, written in the intergrowths of iron-rich and nickel-rich phases that formed during slow cooling. Of intense interest from a magnetic perspective is the "cloudy zone," a nanoscale intergrowth containing tetrataenite-a naturally occurring hard ferromagnetic mineral that has potential applications as a sustainable alternative to rare-earth permanent magnets. Here we use a combination of high-resolution electron diffraction, electron tomography, atom probe tomography (APT), and micromagnetic simulations to reveal the 3D architecture of the cloudy zone with subnanometer spatial resolution and model the mechanism of remanence acquisition during slow cooling on the meteorite parent body. Isolated islands of tetrataenite are embedded in a matrix of an ordered superstructure. The islands are arranged in clusters of three crystallographic variants, which control how magnetic information is encoded into the nanostructure. The cloudy zone acquires paleomagnetic remanence via a sequence of magnetic domain state transformations (vortex to two domain to single domain), driven by Fe-Ni ordering at 320 °C. Rather than remanence being recorded at different times at different positions throughout the cloudy zone, each subregion of the cloudy zone records a coherent snapshot of the magnetic field that was present at 320 °C. Only the coarse and intermediate regions of the cloudy zone are found to be suitable for paleomagnetic applications. The fine regions, on the other hand, have properties similar to those of rare-earth permanent magnets, providing potential routes to synthetic tetrataenite-based magnetic materials.

Functional Group Mapping by Electron Beam Vibrational Spectroscopy from Nanoscale Volumes.

Vibrational spectroscopies directly record details of bonding in materials, but spatially resolved methods have been limited to surface techniques for mapping functional groups at the nanoscale. Electron energy loss spectroscopy (EELS) in the scanning transmission electron microscope presents a route to functional group analysis from nanoscale volumes using transmitted subnanometer electron probes. Here, we now use vibrational EELS to map distinct carboxylate and imidazolate linkers in a metal-organic framework (MOF) crystal-glass composite material. Domains <100 nm in size are observed using vibrational EELS, with recorded spatial resolution <15 nm at interfaces in the composite. This nanoscale functional group mapping is confirmed by correlated EELS at core ionization edges as well as X-ray energy dispersive spectroscopy for elemental mapping of the metal centers of the two constituent MOFs. These results present a complete nanoscale analysis of the building blocks of the MOF composite and establish spatially resolved functional group analysis using electron beam spectroscopy for crystalline and amorphous organic and metal-organic solids.

The Impact of Environmental Conditions on Player Loads During Preseason Training Sessions in Women's Soccer Athletes.

ABSTRACT: Austin, AB, Collins, SM, Huggins, RA, Smith, BA, and Bowman, TG. The impact of environmental conditions on player loads during preseason training sessions in women's soccer athletes. J Strength Cond Res 35(10): 2775-2782, 2021-Our objective was to determine the impact of environmental conditions on player loads during preseason training sessions in women's soccer athletes. Eleven women's NCAA Division III soccer players (age = 20 ± 1 year, height = 167.28 ± 8.65 cm, body mass = 60.18 ± 5.42 kg, V̇o2max = 43.70 ± 3.95 ml·kg-1·min-1) volunteered to wear Global Positioning System (GPS) devices (Sports Performance Tracking, Melbourne, Australia) that provided measures of training session external intensity throughout all preseason practices (n = 15). We recorded wet-bulb globe temperature (WBGT), session Rating of Perceived Exertion-Training Load (sRPE-TL), and ΔBM during each preseason training session and set α ≤ 0.05. The combination of WBGT, sRPE-TL, and ΔBM explained 34% of the variance in GPS-based intensity score (proprietary measure) (F3,153 = 26.25, p < 0.001). Wet-bulb globe temperature (t156 = -2.58, p = 0.01), sRPE (t156 = 8.24, p < 0.001), and ΔBM (t156 = 2.39, p = 0.02) were significantly associated with intensity. The ΔBM from prepractice (60.00 ± 5.21 kg) to postpractice (59.61 ± 5.10 kg) was statistically significant (p < 0.001); however, ΔBM from the beginning of preseason (59.87 ± 5.31 kg) to the end of preseason (59.91 ± 5.58 kg) was not significant (p = 0.89). Despite relatively low to moderate environmental conditions, increases in WBGT were associated with reductions in GPS intensity and elevated internal load via sRPE-TL. Our findings support the association between exercise intensity and WBGT, internal load, and hydration status; thus, coaches and exercise scientists should take these factors into account when monitoring or interpreting intensity metrics. Furthermore, these findings support the continued use of environmental monitoring and hydration best-practice policies to limit exercise intensity in the heat so as to mitigate excessive heat stress.

Direct Imaging of Correlated Defect Nanodomains in a Metal-Organic Framework.

Defect engineering can enhance key properties of metal-organic frameworks (MOFs). Tailoring the distribution of defects, for example in correlated nanodomains, requires characterization across length scales. However, a critical nanoscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the subnanometer imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap uniquely enabling both nanoscale crystallographic analysis and the low-dose formation of multiple diffraction contrast images for defect analysis in MOFs. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or "microstructure", in functional MOF design.

Analysis of complex, beam-sensitive materials by transmission electron microscopy and associated techniques.

We review the use of transmission electron microscopy (TEM) and associated techniques for the analysis of beam-sensitive materials and complex, multiphase systems in-situ or close to their native state. We focus on materials prone to damage by radiolysis and explain that this process cannot be eliminated or switched off, requiring TEM analysis to be done within a dose budget to achieve an optimum dose-limited resolution. We highlight the importance of determining the damage sensitivity of a particular system in terms of characteristic changes that occur on irradiation under both an electron fluence and flux by presenting results from a series of molecular crystals. We discuss the choice of electron beam accelerating voltage and detectors for optimizing resolution and outline the different strategies employed for low-dose microscopy in relation to the damage processes in operation. In particular, we discuss the use of scanning TEM (STEM) techniques for maximizing information content from high-resolution imaging and spectroscopy of minerals and molecular crystals. We suggest how this understanding can then be carried forward for in-situ analysis of samples interacting with liquids and gases, provided any electron beam-induced alteration of a specimen is controlled or used to drive a chosen reaction. Finally, we demonstrate that cryo-TEM of nanoparticle samples snap-frozen in vitreous ice can play a significant role in benchmarking dynamic processes at higher resolution. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites.

Metal-organic framework crystal-glass composites (MOF-CGCs) are materials in which a crystalline MOF is dispersed within a MOF glass. In this work, we explore the room-temperature stabilization of the open-pore form of MIL-53(Al), usually observed at high temperature, which occurs upon encapsulation within a ZIF-62(Zn) MOF glass matrix. A series of MOF-CGCs containing different loadings of MIL-53(Al) were synthesized and characterized using X-ray diffraction and nuclear magnetic resonance spectroscopy. An upper limit of MIL-53(Al) that can be stabilized in the composite was determined for the first time. The nanostructure of the composites was probed using pair distribution function analysis and scanning transmission electron microscopy. Notably, the distribution and integrity of the crystalline component in a sample series were determined, and these findings were related to the MOF-CGC gas adsorption capacity in order to identify the optimal loading necessary for maximum CO2 sorption capacity.

Decoration of plasmonic Mg nanoparticles by partial galvanic replacement.

Plasmonic structures have attracted much interest in science and engineering disciplines, exploring a myriad of potential applications owing to their strong light-matter interactions. Recently, the plasmonic concentration of energy in subwavelength volumes has been used to initiate chemical reactions, for instance by combining plasmonic materials with catalytic metals. In this work, we demonstrate that plasmonic nanoparticles of earth-abundant Mg can undergo galvanic replacement in a nonaqueous solvent to produce decorated structures. This method yields bimetallic architectures where partially oxidized 200-300 nm Mg nanoplates and nanorods support many smaller Au, Ag, Pd, or Fe nanoparticles, with potential for a stepwise process introducing multiple decoration compositions on a single Mg particle. We investigated this mechanism by electron-beam imaging and local composition mapping with energy-dispersive X-ray spectroscopy as well as, at the ensemble level, by inductively coupled plasma mass spectrometry. High-resolution scanning transmission electron microscopy further supported the bimetallic nature of the particles and provided details of the interface geometry, which includes a Mg oxide separation layer between Mg and the other metal. Depending on the composition of the metallic decorations, strong plasmonic optical signals characteristic of plasmon resonances were observed in the bulk with ultraviolet-visible spectrometry and at the single particle level with darkfield scattering. These novel bimetallic and multimetallic designs open up an exciting array of applications where one or multiple plasmonic structures could interact in the near-field of earth-abundant Mg and couple with catalytic nanoparticles for applications in sensing and plasmon-assisted catalysis.

Atom-by-Atom Resolution of Structure-Function Relations over Low-Nuclearity Metal Catalysts.

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application-dependent requirements of the active ensemble. In the semi-hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well-defined numbers of atoms.

Subwavelength Spatially Resolved Coordination Chemistry of Metal-Organic Framework Glass Blends.

Microstructured metal-organic framework (MOF) glasses have been produced by combining two amorphous MOFs. However, the electronic structure of these materials has not been interrogated at the length scales of the chemical domains formed in these glasses. Here, we report a subwavelength spatially resolved physicochemical analysis of the electronic states at visible and UV energies in a blend of two zeolitic imidazolate frameworks (ZIFs), ZIF-4-Co and ZIF-62-Zn. By combining spectroscopy at visible and UV energies as well as at core ionization energies in electron energy loss spectroscopy in the scanning transmission electron microscope with density functional theory calculations, we show that domains less than 200 nm in size retain the electronic structure of the precursor crystalline ZIF phases. Prototypical signatures of coordination chemistry including d- d transitions in ZIF-4-Co are assigned and mapped with nanoscale precision.

Neocortical SHANK1 regulation of forebrain dependent associative learning.

Learning-induced neocortical synaptic plasticity is a well-established mechanism mediating memory consolidation. Classic learning paradigms elicit synaptic changes in various brain regions including the neocortex. Work from our laboratory has further suggested synaptic remodeling in primary somatosensory cortex (S1) during forebrain-dependent associative learning. While this process of synaptic remodeling is largely believed to contribute to memory consolidation, the underlying processes mediating this plasticity are poorly understood. Interestingly, abnormal expression of the synaptic scaffolding protein SHANK1 has been linked with aberrant synaptic plasticity and learning impairments, suggesting that it plays a critical role in these processes. However, a direct analysis of the role for SHANK1 during learning in the neocortex, the most likely site for memory storage, has never been adequately explored. To directly examine SHANK1's potential role during learning and memory, the following study set out to both examine neocortical SHANK1 expression during a learning event and determine the consequences of reducing neocortical SHANK1 expression on learning. The current study found that SHANK1 expression is transiently increased during periods of learning-induced dendritic spine plasticity in the neocortex. Furthermore, shRNA-mediated neocortical SHANK1 knockdown significantly impairs acquisition for the forebrain-dependent associative learning task (whisker-trace-eyeblink conditioning). Consistent with these findings, SHANK1 has been implicated in various neurological disorders. Collectively, these findings suggest a role for SHANK1 in neocortical learning-induced dendritic spine plasticity underlying learning and normal cognition; thus, providing potential insight into neurological mechanisms mediating abnormalities of impaired cognition.

Changes of general fitness and muscle properties following police cadet training.

[Purpose] This study was performed to examine the relationship between physical performance and muscle properties during police cadet training. The study's hypothesis was that improved physical performance brought about by training, would in turn cause a reduction in muscle flexibility. [Subjects and Methods] Fifty-nine police cadets were included in this study. Standard fitness tests and quantitative assessments of muscular biomechanical properties were conducted before, during and after the 20-week cadet training. [Results] General fitness had improved at the end of the police cadet training. There was no significant decrease in muscle flexibility as measured by the Sit-and-Reach test. However, muscle compliance of the non-dominant leg measured by the relaxation coefficient had decreased at the end of the police cadet training. [Conclusion] The increased sit-and-reach distance could be due in part to strengthening of the abdominal muscles. On the other hand, the biomechanical test, which was specific to muscle extensibility, showed a reduction in the relaxation coefficient of the non-dominant leg. Our data suggests that changes in muscle compliance as a result of lower extremity training should be considered. This data may be useful in the design of a training protocol that prevents the potential injuries caused by reduced muscle flexibility.

Qualitative multiplatform microanalysis of individual heterogeneous atmospheric particles from high-volume air samples.

High-resolution microscopic analysis of individual atmospheric particles can be difficult, because the filters upon which particles are captured are often not suitable as substrates for microscopic analysis. Described here is a multiplatform approach for microscopically assessing chemical and optical properties of individual heterogeneous urban dust particles captured on fibrous filters during high-volume air sampling. First, particles embedded in fibrous filters are transferred to polished silicon or germanium wafers with electrostatically assisted high-speed centrifugation. Particles are clustered in an array of deposit areas, which allows for easily locating the same particle with different microscopy instruments. Second, particles with light-absorbing and/or light-scattering behavior are identified for further study from bright-field and dark-field light-microscopy modes, respectively. Third, particles identified from light microscopy are compositionally mapped at high definition with field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. Fourth, compositionally mapped particles are further analyzed with focused ion-beam (FIB) tomography, whereby a series of thin slices from a particle are imaged, and the resulting image stack is used to construct a three-dimensional model of the particle. Finally, particle chemistry is assessed over two distinct regions of a thin FIB slice of a particle with energy-filtered transmission electron microscopy (TEM) and electron energy-loss spectroscopy associated with scanning transmission electron microscopy (STEM).

The relationship between body composition and preseason performance tests of collegiate male lacrosse players.

Numerous studies have examined the effects that body composition has on performance in football, soccer, and ice hockey; yet, there are no similar studies examining this relationship in men's lacrosse. The purpose of the study was to examine the physiological profiles and the relationship between body composition and performance in aerobic and anaerobic tests. Fifty-four (19.63 ± 1.21 years; 178.53 ± 6.17 cm; 81.66 ± 14.96 kg) Division III intercollegiate athletes participated. Performance tests, including a 1 repetition maximum power clean (PC), body weight (lbs), bench press repetitions, parallel bar triceps dips to fatigue (DR), two 300-yard shuttles, and a 1-mile run (MT), were completed after the completion of fall preseason practices. Body composition was estimated using air-displacement plethysmography. Correlation coefficients determined relationships between percent body fat (%BF), fat-free mass (FFM), and testing variables. Increased %BF was negatively correlated to DR (r = -0.36, p = 0.01) whereas positively correlated to each 300-yard shuttle time (T1 and T2), total 300-yard shuttle time (TT), and MT (r = 0.64, p = 0.00; r = 0.68, p = 0.00; r = 0.69, p = 0.00; and r = 0.44, p = 0.00, respectively). Increased FFM was positively correlated with PC (r = 0.58, p = 0.00) yet not correlated (p ≥ 0.05) with other variables. Results indicated that increased %BF might be a detriment to the repetitive anaerobic performance and aerobic capacity vital to on-field lacrosse performance. Body composition also demonstrated a significant relationship to moving internal vs. external resistances.

The Effects of a Core Stabilization Training Program on the Performance of Functional Tasks in Firefighters.

The purpose of this study was to observe if core stabilization training plays a significant role in firefighter time-to-completion during a functional performance test. A within subjects study design was used in which subjects (n = 13, 84.6% male, 33.7 ± 7.4 years of age, 91.06 ± 13.29 kg, 25.79 ± 6.55 percent body fat, 8.96 ± 7.51 years of firefighting experience) completed two performance tests (pre and post core training), comprised of 7 firefighter-specific exercises performed while wearing a 22.68 kg weight vest to mimic typical firefighter equipment. Between testing sessions, subjects were prescribed specific core stabilization exercises to perform at least three days a week for a total of 4 weeks. Time-to-completion was significantly quicker between the first (300.89 ± 42.11s) and second (256.92 ± 34.31s) performance testing, on average by 43.8 seconds (p < 0.001). Body mass index (p = 0.065) and rating of perceived exertion during testing (p = 0.084) did not significantly decrease across the course of the study. Adequate fitness is essential to firefighters' job task performance. Data from this study suggests that regular core stabilization training may assist in optimizing the effectiveness, and potentially safety, of firefighters' performance in high intensity functional skills.