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639 result(s) for "Beale, Andrew"
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Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes
The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell’s performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded Li x Mn 2 O 4 electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO 2 within the first cycle. Other particles contain monoclinic Li 2 MnO 3 near the surface and almost pure spinel Li x Mn 2 O 4 near the core. Following 150 cycles, concentrations of LiMnO 2 and Li 2 MnO 3 significantly increase and widely vary between particles. Dynamic chemical and structural heterogeneities within electrodes are known to lead to battery degradation and failure. Here, the authors show that X-ray diffraction computed tomography can be used to spatially quantify the dynamic crystallographic states of electrodes as they operate and degrade.
Design of next-generation ceramic fuel cells and real-time characterization with synchrotron X-ray diffraction computed tomography
Ceramic fuel cells offer a clean and efficient means of producing electricity through a variety of fuels. However, miniaturization of cell dimensions for portable device application remains a challenge, as volumetric power densities generated by readily-available planar/tubular ceramic cells are limited. Here, we demonstrate a concept of ‘micro-monolithic’ ceramic cell design. The mechanical robustness and structural integrity of this design is thoroughly investigated with real-time, synchrotron X-ray diffraction computed tomography, suggesting excellent thermal cycling stability. The successful miniaturization results in an exceptional power density of 1.27 W cm −2 at 800 °C, which is among the highest reported. This holistic design incorporates both mechanical integrity and electrochemical performance, leading to mechanical property enhancement and representing an important step toward commercial development of portable ceramic devices with high volumetric power (>10 W cm −3 ), fast thermal cycling and marked mechanical reliability. Miniaturized ceramic fuel cells are attractive for portable devices, but performance should be optimized. Here the authors report a micro-monolithic ceramic cell design for a tubular solid oxide fuel cell containing a multi-channel anode support with enhanced power density and stable operation.
Macromolecular condensation buffers intracellular water potential
Optimum protein function and biochemical activity critically depends on water availability because solvent thermodynamics drive protein folding and macromolecular interactions 1 . Reciprocally, macromolecules restrict the movement of ‘structured’ water molecules within their hydration layers, reducing the available ‘free’ bulk solvent and therefore the total thermodynamic potential energy of water, or water potential. Here, within concentrated macromolecular solutions such as the cytosol, we found that modest changes in temperature greatly affect the water potential, and are counteracted by opposing changes in osmotic strength. This duality of temperature and osmotic strength enables simple manipulations of solvent thermodynamics to prevent cell death after extreme cold or heat shock. Physiologically, cells must sustain their activity against fluctuating temperature, pressure and osmotic strength, which impact water availability within seconds. Yet, established mechanisms of water homeostasis act over much slower timescales 2 , 3 ; we therefore postulated the existence of a rapid compensatory response. We find that this function is performed by water potential-driven changes in macromolecular assembly, particularly biomolecular condensation of intrinsically disordered proteins. The formation and dissolution of biomolecular condensates liberates and captures free water, respectively, quickly counteracting thermal or osmotic perturbations of water potential, which is consequently robustly buffered in the cytoplasm. Our results indicate that biomolecular condensation constitutes an intrinsic biophysical feedback response that rapidly compensates for intracellular osmotic and thermal fluctuations. We suggest that preserving water availability within the concentrated cytosol is an overlooked evolutionary driver of protein (dis)order and function. Water thermodynamics drive changes in macromolecular assembly that rapidly restore intracellular water availability in response to physiological fluctuations in temperature, pressure and osmotic strength.
Tuning of catalytic sites in Pt/TiO2 catalysts for the chemoselective hydrogenation of 3-nitrostyrene
The catalytic activities of supported metal nanoparticles can be tuned by appropriate design of synthesis strategies. Each step in a catalyst synthesis method can play an important role in preparing the most efficient catalyst. Here we report the careful manipulation of the post-synthetic heat treatment procedure—together with control over the metal loading—to prepare a highly efficient 0.2 wt% Pt/TiO 2 catalyst for the chemoselective hydrogenation of 3-nitrostyrene. For Pt/TiO 2 catalysts with 0.2 and 0.5 wt% loading levels, reduction at 450 °C induces the coverage of TiO x over Pt nanoparticles through a strong metal–support interaction, which is detrimental to their catalytic activities. However, this can be avoided by following calcination treatment with reduction (both at 450 °C), allowing us to prepare an exceptionally active catalyst. Detailed characterization has revealed that the peripheral sites at the Pt/TiO 2 interface are the most likely active sites for this hydrogenation reaction. Small changes in catalyst synthesis can have large and often poorly understood effects on activity. Here the authors show how variation of post synthetic heat treatment—in combination with changes in metal loadings—can lead to the most efficient catalysts, and also identify the most likely active sites.
Compensatory ion transport buffers daily protein rhythms to regulate osmotic balance and cellular physiology
Between 6–20% of the cellular proteome is under circadian control and tunes mammalian cell function with daily environmental cycles. For cell viability, and to maintain volume within narrow limits, the daily variation in osmotic potential exerted by changes in the soluble proteome must be counterbalanced. The mechanisms and consequences of this osmotic compensation have not been investigated before. In cultured cells and in tissue we find that compensation involves electroneutral active transport of Na + , K + , and Cl − through differential activity of SLC12A family cotransporters. In cardiomyocytes ex vivo and in vivo, compensatory ion fluxes confer daily variation in electrical activity. Perturbation of soluble protein abundance has commensurate effects on ion composition and cellular function across the circadian cycle. Thus, circadian regulation of the proteome impacts ion homeostasis with substantial consequences for the physiology of electrically active cells such as cardiomyocytes. Osmotic compensation by electroneutral ion transport buffers TORC1-mediated changes in the cytosolic proteome, and maintains intracellular homeostasis and cell volume over the circadian cycle. Here, the authors find such ion content changes drive daily rhythms in cardiomyocyte electrical activity.
Ten–Second Electrophysiology: Evaluation of the 3DEP Platform for high-speed, high-accuracy cell analysis
Electrical correlates of the physiological state of a cell, such as membrane conductance and capacitance, as well as cytoplasm conductivity, contain vital information about cellular function, ion transport across the membrane, and propagation of electrical signals. They are, however, difficult to measure; gold-standard techniques are typically unable to measure more than a few cells per day, making widespread adoption difficult and limiting statistical reproducibility. We have developed a dielectrophoretic platform using a disposable 3D electrode geometry that accurately (r 2  > 0.99) measures mean electrical properties of populations of ~20,000 cells, by taking parallel ensemble measurements of cells at 20 frequencies up to 45 MHz, in (typically) ten seconds. This allows acquisition of ultra-high-resolution (100-point) DEP spectra in under two minutes. Data acquired from a wide range of cells – from platelets to large cardiac cells - benchmark well with patch-clamp-data. These advantages are collectively demonstrated in a longitudinal (same-animal) study of rapidly-changing phenomena such as ultradian (2–3 hour) rhythmicity in whole blood samples of the common vole ( Microtus arvalis ), taken from 10 µl tail-nick blood samples and avoiding sacrifice of the animal that is typically required in these studies.
Intracellular potassium levels orchestrate circadian rhythmicity and cell division
Circadian (~24 h) rhythms are a fundamental feature of life, and their disruption increases the risk of infectious diseases, metabolic disorders, and cancer. We previously identified circadian oscillations in intracellular potassium concentrations in cells across kingdoms. Using highly divergent eukaryotic cell types, we now show that potassium levels act to regulate the period and phase of clock gene expression rhythms, therefore establishing intracellular potassium as a bona fide regulator of cellular circadian rhythms. Intracellular potassium also regulates critical events in the cell cycle. Strikingly, we observe that manipulating potassium levels inhibits cell proliferation in a circadian phase-dependent manner. As the timing of cell division is tuned by the circadian clock, we hypothesised that potassium rhythms could mechanistically link cell proliferation rhythms to the circadian cycle. In line with this hypothesis, we find that potassium levels are not only sufficient to instruct the timing of cell proliferation, but also essential to maintain coherent coupling between circadian rhythms and proliferation rhythms. These results establish circadian potassium rhythms as a primary factor coupling the cell- and circadian cycles in eukaryotic cells. Circadian rhythms are ~24-hour biological cycles that influence processes from immunity to metabolism, and this study explores how intracellular potassium contributes to their regulation. The authors show that potassium levels actively set the period and phase of clock gene rhythms and are essential for coupling circadian timing to cell-division cycles, making potassium an important regulator linking the circadian and cell cycles.
Eukaryotic cell biology is temporally coordinated to support the energetic demands of protein homeostasis
Yeast physiology is temporally regulated, this becomes apparent under nutrient-limited conditions and results in respiratory oscillations (YROs). YROs share features with circadian rhythms and interact with, but are independent of, the cell division cycle. Here, we show that YROs minimise energy expenditure by restricting protein synthesis until sufficient resources are stored, while maintaining osmotic homeostasis and protein quality control. Although nutrient supply is constant, cells sequester and store metabolic resources via increased transport, autophagy and biomolecular condensation. Replete stores trigger increased H + export which stimulates TORC1 and liberates proteasomes, ribosomes, chaperones and metabolic enzymes from non-membrane bound compartments. This facilitates translational bursting, liquidation of storage carbohydrates, increased ATP turnover, and the export of osmolytes. We propose that dynamic regulation of ion transport and metabolic plasticity are required to maintain osmotic and protein homeostasis during remodelling of eukaryotic proteomes, and that bioenergetic constraints selected for temporal organisation that promotes oscillatory behaviour. Yeast exhibit oscillations that share features with circadian rhythms. The authors show that bioenergetic constraints promote oscillatory behaviour: resources are stored until supplies can support translational bursting, this is licensed by ion transport and release from membrane-less compartments.
A deep convolutional neural network for real-time full profile analysis of big powder diffraction data
We present Parameter Quantification Network (PQ-Net), a regression deep convolutional neural network providing quantitative analysis of powder X-ray diffraction patterns from multi-phase systems. The network is tested against simulated and experimental datasets of increasing complexity with the last one being an X-ray diffraction computed tomography dataset of a multi-phase Ni-Pd/CeO2-ZrO2/Al2O3 catalytic material system consisting of ca. 20,000 diffraction patterns. It is shown that the network predicts accurate scale factor, lattice parameter and crystallite size maps for all phases, which are comparable to those obtained through full profile analysis using the Rietveld method, also providing a reliable uncertainty measure on the results. The main advantage of PQ-Net is its ability to yield these results orders of magnitude faster showing its potential as a tool for real-time diffraction data analysis during in situ/operando experiments.
Mosquito feeding behavior and how it influences residual malaria transmission across Africa
The antimalarial efficacy of the most important vector control interventions—long-lasting insecticidal nets (LLINs) and indoor residual spraying (IRS)—primarily protect against mosquitoes’ biting people when they are in bed and indoors. Mosquito bites taken outside of these times contribute to residual transmission which determines the maximum effectiveness of current malaria prevention. The likelihood mosquitoes feed outside the time of day when LLINs and IRS can protect people is poorly understood, and the proportion of bites received outdoors may be higher after prolonged vector control. A systematic review of mosquito and human behavior is used to quantify and estimate the public health impact of outdoor biting across Africa. On average 79% of bites by the major malaria vectors occur during the time when people are in bed. This estimate is substantially lower than previous predictions, with results suggesting a nearly 10% lower proportion of bites taken at the time when people are beneath LLINs since the year 2000. Across Africa, this higher outdoor transmission is predicted to result in an estimated 10.6 million additional malaria cases annually if universal LLIN and IRS coverage was achieved. Higher outdoor biting diminishes the cases of malaria averted by vector control. This reduction in LLIN effectiveness appears to be exacerbated in areas where mosquito populations are resistant to insecticides used in bed nets, but no association was found between physiological resistance and outdoor biting. Substantial spatial heterogeneity in mosquito biting behavior between communities could contribute to differences in effectiveness of malaria control across Africa.