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We present a structural and magnetic study of two batches of polycrystalline LiNi0.8Mn0.1Co0.1O2 (commonly known as Li NMC 811), a Ni-rich Li ion battery cathode material, using elemental analysis, X-ray and neutron diffraction, magnetometry, and polarized neutron scattering measurements. We find that the samples, labeled S1 and S2, have the composition Li1-xNi0.9+x-yMnyCo0.1O2, with x = 0.025(2), y = 0.120(2) for S1 and x = 0.002(2), y = 0.094(2) for S2, corresponding to different concentrations of magnetic ions and excess Ni2+ in the Li+ layers. Both samples show a peak in the zero-field-cooled (ZFC) dc susceptibility at 8.0(2) K, but the temperature at which the ZFC and FC (field-cooled) curves deviate is substantially different: 64(2) K for S1 and 122(2) K for S2. The ac susceptibility measurements show that the transition for S1 shifts with frequency whereas no such shift is observed for S2 within the resolution of our measurements. Our results demonstrate the sample dependence of magnetic properties in Li NMC 811, consistent with previous reports on the parent material LiNiO2. We further establish that a combination of experimental techniques is necessary to accurately determine the chemical composition of next-generation battery materials with multiple cations.
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The selective hybridization of DNA is of key importance for many practical applications such as gene detection and DNA-mediated self-assembly. These applications require a quantitative prediction of the hybridization free energy. Existing methods ignore the effects of non-complementary ssDNA tails beyond the first unpaired base. We use experiments and simulations to show that the binding strength of complementary ssDNA oligomers is altered by these sequences of non-complementary nucleotides. Even a small number of non-binding bases are enough to raise the hybridization free energy by approximately 1 kcal/mol at physiological salt concentrations. We propose a simple analytical expression that accounts quantitatively for this variation as a function of tail length and salt concentration.
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ADN/química , Hibridación de Ácido Nucleico , TermodinámicaRESUMEN
The cathode-electrolyte interphase (CEI) in Li-ion batteries plays a key role in suppressing undesired side reactions while facilitating Li-ion transport. Ni-rich layered cathode materials offer improved energy densities, but their high interfacial reactivities can negatively impact the cycle life and rate performance. Here we investigate the role of electrolyte salt concentration, specifically LiPF6 (0.5-5 m), in altering the interfacial reactivity of charged LiN0.8Mn0.1Co0.1O2 (NMC811) cathodes in standard carbonate-based electrolytes (EC/EMC vol %/vol % 3:7). Extended potential holds of NMC811/Li4Ti5O12 (LTO) cells reveal that the parasitic electrolyte oxidation currents observed are strongly dependent on the electrolyte salt concentration. X-ray photoelectron and absorption spectroscopy (XPS/XAS) reveal that a thicker LixPOyFz-/LiF-rich CEI is formed in the higher concentration electrolytes. This suppresses reactions with solvent molecules resulting in a thinner, or less-dense, reduced surface layer (RSL) with lower charge transfer resistance and lower oxidation currents at high potentials. The thicker CEI also limits access of acidic species to the RSL suppressing transition-metal dissolution into the electrolyte, as confirmed by nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). This provides insight into the main degradation processes occurring at Ni-rich cathode interfaces in contact with carbonate-based electrolytes and how electrolyte formulation can help to mitigate these.
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Background: Declines in biodiversity and ecosystem health due to climate change are raising urgent concerns. In response, large-scale multispecies monitoring programmes are being implemented that increasingly adopt sensor-based approaches such as acoustic recording. These approaches rely heavily on ecological data science. However, developing reliable algorithms for processing sensor-based data relies heavily on labelled datasets of sufficient quality and quantity. We present a dataset of 1,575 dawn chorus soundscape recordings, 141 being fully annotated (n = 32,994 annotations) with avian, mammalian and amphibian vocalisations. The remaining recordings were included to facilitate novel research applications. These recordings are paired with 48 site-level climatic, forest structure and topographic covariates. This dataset provides a valuable resource to researchers developing acoustic classification algorithms or studying biodiversity and wildlife behaviour and its relationship to environmental gradients. The dawn chorus recordings were collected as part of a long-term Northern Spotted Owl monitoring program; this demonstrates the complementary value of harnessing existing monitoring efforts to strengthen biodiversity sampling. New information: This dataset of dawn chorus soundscape recordings is one of the few open-access acoustic datasets annotated with non-biotic and both interspecific (across species) and intraspecific (within species) bird, mammal and amphibian sonotypes and the first that is paired with climatic, forest structure and topographical covariates extracted at recorder locations. This makes it a valuable resource for researchers studying the dawn chorus and its relationship to the environment.
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We demonstrate the realization of a two-dimensional chiral optical waveguide with an infinite translational symmetry that exhibits asymmetric wave propagation. The low-symmetry geometry of the cross-section that lacks any rotational and mirror symmetries shows in-principal directional asymmetric polarization rotation. We use general symmetry arguments to provide qualitative analysis of the waveguide's eigenstates and numerically corroborate this using finite element simulation. We show that despite the only perturbative break of time-reversal symmetry via small modal losses, the structure supports a non-degenerate pair of co-rotating elliptical modes. We fabricated meters long fiber with a spiral structure and studied its optical properties.
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Tecnología de Fibra Óptica/instrumentación , Tecnología de Fibra Óptica/métodos , Modelos Teóricos , Refractometría/instrumentación , Dispersión de Radiación , Simulación por Computador , Diseño Asistido por Computadora , Diseño de Equipo , Análisis de Falla de Equipo , LuzRESUMEN
Nickel-rich layered oxide cathodes such as NMC811 (LixNi0.8Mn0.1Co0.1O2) currently have the highest practical capacities of cathodes used commercially, approaching 200 mAh/g. Lithium is removed from NMC811 via a solid-solution behavior when delithiated to xLi > 0.10, maintaining the same layered (O3 structure) throughout as observed via operando diffraction measurements. Although it is possible to further delithiate NMC811, it is kinetically challenging, and there are significant side reactions between the electrolyte and cathode surface. Here, small format, NMC811-graphite pouch cells were charged to high voltages at elevated temperatures and held for days to access high states of delithiation. Rietveld refinements on high-resolution diffraction data and indexing of selected area electron diffraction patterns, both acquired ex situ, show that NMC811 undergoes a partial and reversible transition from the O3 to the O1 phase under these conditions. The O1 phase fraction depends not only on the concentration of intercalated lithium but also on the hold temperature and hold time, indicating that the phase transition is kinetically controlled. 1H NMR spectroscopy shows that the proton concentration decreases with O1 phase fraction and is not, therefore, likely to be driving the O3-O1 phase transition.
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Aging and many illnesses and injuries impair skeletal muscle mass and function, but the molecular mechanisms are not well understood. To better understand the mechanisms, we generated and studied transgenic mice with skeletal muscle-specific expression of growth arrest and DNA damage inducible α (GADD45A), a signaling protein whose expression in skeletal muscle rises during aging and a wide range of illnesses and injuries. We found that GADD45A induced several cellular changes that are characteristic of skeletal muscle atrophy, including a reduction in skeletal muscle mitochondria and oxidative capacity, selective atrophy of glycolytic muscle fibers, and paradoxical expression of oxidative myosin heavy chains despite mitochondrial loss. These cellular changes were at least partly mediated by MAP kinase kinase kinase 4, a protein kinase that is directly activated by GADD45A. By inducing these changes, GADD45A decreased the mass of muscles that are enriched in glycolytic fibers, and it impaired strength, specific force, and endurance exercise capacity. Furthermore, as predicted by data from mouse models, we found that GADD45A expression in skeletal muscle was associated with muscle weakness in humans. Collectively, these findings identify GADD45A as a mediator of mitochondrial loss, atrophy, and weakness in mouse skeletal muscle and a potential target for muscle weakness in humans.
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Mitocondrias Musculares , Músculo Esquelético , Atrofia Muscular , Animales , Humanos , Ratones , Envejecimiento , Proteínas de Ciclo Celular/genética , Proteínas de Ciclo Celular/metabolismo , Mitocondrias Musculares/metabolismo , Debilidad Muscular/metabolismo , Músculo Esquelético/metabolismo , Atrofia Muscular/patologíaRESUMEN
We demonstrate the preparation and transmission of the lowest loss azimuthally polarized TE01â like mode in a photonic band gap (PBG) fiber. Using the nature of the mode and the properties of the band gap structure we construct a novel coupler that operates away from the band gap's center to enhance the differential losses and facilitate the radiative loss of hybrid fundamental fiber modes. Remarkably, even though the coupler is highly multimoded, a pure azimuthally polarized mode is generated after only 17 cm. Theoretical calculations verify the validity of this technique and accurately predict the coupling efficiency. The generation and single mode propagation of this unique azimuthally polarized, doughnut shaped mode in a large hollow-core fiber can find numerous applications including in optical microscopy, optical tweezers, and guiding particles along the fiber.
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Tecnología de Fibra Óptica/instrumentación , Refractometría/instrumentación , Anisotropía , Diseño de Equipo , Análisis de Falla de Equipo , Luz , Dispersión de RadiaciónRESUMEN
Improved analytical tools are urgently required to identify degradation and failure mechanisms in Li-ion batteries. However, understanding and ultimately avoiding these detrimental mechanisms requires continuous tracking of complex electrochemical processes in different battery components. Here, we report an operando spectroscopy method that enables monitoring the chemistry of a carbonate-based liquid electrolyte during electrochemical cycling in Li-ion batteries with a graphite anode and a LiNi0.8Mn0.1Co0.1O2 cathode. By embedding a hollow-core optical fibre probe inside a lab-scale pouch cell, we demonstrate the effective evolution of the liquid electrolyte species by background-free Raman spectroscopy. The analysis of the spectroscopy measurements reveals changes in the ratio of carbonate solvents and electrolyte additives as a function of the cell voltage and show the potential to track the lithium-ion solvation dynamics. The proposed operando methodology contributes to understanding better the current Li-ion battery limitations and paves the way for studies of the degradation mechanisms in different electrochemical energy storage systems.
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Hollow-core photonic bandgap fibers (PBG) offer the opportunity to suppress highly the optical absorption and nonlinearities of their constituent materials, which makes them viable candidates for transmitting high-peak power pulses. We report the fabrication and characterization of polymer-composite PBG fibers in a novel materials system, polycarbonate and arsenic sulfide glass. Propagation losses for the 60 microm-core fibers are less than 2dB/m, a 52x improvement over previous 1D-PBG fibers at this wavelength. Through preferential coupling the fiber is capable of operating with over 97% the fiber's power output in the fundamental (HE(11)) mode. The fiber transmitted pulses with peak powers of 11.4 MW before failure.