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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Influence of the Defect Stability on n-Type Conductivity in Electron-Doped [alpha]- and [beta]-Co(OH
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Discovery of an Orally Bioavailable and Selective PKMYT1 Inhibitor, RP-6306
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Identification of RP-6685, an Orally Bioavailable Compound that Inhibits the DNA Polymerase Activity
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Electrostatic Work Causes Unexpected Reactivity in Ionic Photoredox Catalysts in Low Dielectric Constant Solvents
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Reversible Electron Doping of Layered Metal Hydroxide Nanoplates (M = Co, Ni) Using n-Butyllithium
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Unconventional Pressure-Driven Metamagnetic Transitions in Topological van der Waals Magnets
Activating metamagnetic transitions between ordered states in van der Waals magnets and devices bring great opportunities in spintronics. Here we show that external pressure, which enhances the inter-layer hopping without introducing chemical disorders, triggers multiple metamagnetic transitions upon cooling in the topological van der Waals magnets Mn(Bi 1–x Sb x ) 4 Te 7 , where the antiferro magnetic interlayer superexchange coupling competes with the ferromagnetic interlayer coupling mediated by the antisite Mn spins. The temperature-pressure phase diagrams reveal that while the ordering temperature from the paramagnetic to ordered states is almost pressure-independent, the metamagnetic transitions show non-trivial pressure and temperature dependence, even re-entrance. For these highly anisotropic magnets, we attribute the former to the ordering temperature being only weakly dependent on the intralayer parameters, the latter to the parametrically different pressure and temperature dependence of the two interlayer couplings. Our independent probing of these disparate magnetic interactions paves an avenue for efficient magnetic manipulations in van der Waals magnets.
Defect-Limited Mobility and Defect Thermochemistry in Mixed A-Cation Tin Perovskites: (CH3NH3)1-xCsxSnBr3
Hybrid organic-inorganic semiconductors crystallizing in the perovskite structure present a significant opportunity for realizing defect-tolerant semiconductors. In this work, we examine the solid solution, (CH3NH3)1-xCsxSnBr3, and identify the thermochemistry dictating the intrinsic carrier concentrations and how local structural distortions influences this electronic behavior. This family of compounds exhibits the expected systematic trend in decreasing optical gap with the cesium to methylammonium A-site mixing ratio, x, in the visible region. However, the carrier mobility, as determined from time-resolved microwave conductivity measurements, trends opposite to that expected from first-principles calculations combined with Boltzmann scattering theory calculations of the carrier mobility. We propose that this is a result of increasing carrier scattering with x in (CH3NH3)1-xCsxSnBr3 due to a significant increase in the carrier density with x. By examining the dependence of the carrier density as a function of x, we infer the compositional-dependence of the average enthalpy and nonconfigurational entropy per defect. While diffraction reveals a cubic aristotypic perovskite structure as a function of x at room temperature, the pair distribution functions obtained from synchrotron X-ray total scattering from these materials are better described by symmetry-adapted displacement modes of the Pm3m crystal structure, which we attribute to a large degree of anharmonic dynamics of the atom positions. This analysis shows that CH3NH3+-rich compositions retain mostly linear Sn-Br-Sn bonding environments through the displacements, while Cs+-rich compositions lead to more significantly bent Sn-Br-Sn environments. We propose that these bent bonding arrangements in Cs-rich compositions yield a higher propensity for defect formation. This also provides a rationale for carrier trapping that gives rise to anomalous microwave transients. Together, these results provide insight into the structure-dynamics-properties relationships in this highly anharmonic system with high amplitude atomic motions and low defect formation energies.
Tunable Broad Light Emission from 3D “Hollow” Bromide Perovskites through Defect Engineering
We report hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow" perovskites. In this work, we engineered a new family of 3D highly defective yet crystalline "hollow" bromide perovskites with general formula (FA) 1-x (en) x (Pb) 1-0.7x (Br) 3-0.4x (FA = formamidinium (FA + ), en = ethylenediammonium (en 2+ ), x = 0-0.44). Pair distribution function analysis shed light on the local structural coherence, revealing a wide distribution of Pb-Pb distances in the crystal structure as a consequence of the Pb/Br-deficient nature and en inclusion in the lattice. By manipulating the number of Pb/Br vacancies, we finely tune the optical properties of the pristine FAPbBr 3 by blue shifting the band gap from 2.20 to 2.60 eV for the x = 0.42 en sample. A most unexpected outcome was that at x > 0.33 en incorporation, the material exhibits strong broad light emission (1% photoluminescence quantum yield (PLQY)) that is maintained after exposure to air for more than a year. This is the first example of strong broad light emission from a 3D hybrid halide perovskite, demonstrating that meticulous defect engineering is an excellent tool for customizing the optical properties of these semiconductors.
Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites
The emission of white light from a single material is atypical and is of interest for solid-state lighting applications. Broadband light emission has been observed in some layered perovskite derivatives, A 2 PbBr 4 (A = R-NH 3 + ), and correlates with static structural distortions corresponding to out-of-plane tilting of the lead bromide octahedra. While materials with different organic cations can yield distinct out-of-plane tilts, the underlying origin of the octahedral tilting remains poorly understood. Using high energy resolution (e.g., quasi-elastic) neutron scattering, this contribution details the rotational dynamics of the organic cations in A 2 PbBr 4 materials where A = n-butylammonium (nBA), 1,8-diaminooctammonium (ODA), and 4-aminobutyric acid (GABA). The organic cation dynamics differentiate (nBA) 2 PbBr 4 from (ODA)PbBr 4 or (GABA) 2 PbBr 4 in that the larger spatial extent of dynamics of nBA yields a larger effective cation radius. The larger effective volume of the nBA cation in (nBA) 2 PbBr 4 yields a closer to ideal A-site geometry, preventing the out-of-plane tilt and broadband luminescence. In all three compounds, we observe hydrogen dynamics attributed to rotation of the ammonium headgroup and at a time scale faster than the white light photoluminescence studied by time-correlated single photon counting spectroscopy. This supports a previous assignment of the broadband emission as resulting from a single ensemble, such that the emissive excited state experiences many local structures faster than the emissive decay. Furthermore, the findings presented here highlight the role of the organic cation and its dynamics in hybrid organic–inorganic perovskites and white light emission.
Quantitative Determination of Electronic Effects in Free Radicals through Open-Shell Hammett Substituent Constants
Hammett substituent constants (σ), which quantify the electronic effects of functional groups, are widely used for predicting the properties of organic compounds and investigating reaction mechanisms. While these values have been obtained for a wide range of closed-shell substituents, measurements of analogous values for open-shell substituents are rare due to challenges associated with their short lifetimes. Here, in this report, we developed a combined experimental and computational approach for quantifying the electronic properties of open-shell substituents based on changes in nitrile vibrational frequencies (ν(C≡N)). By coupling pulse radiolysis and time-resolved infrared spectroscopy (PR-TRIR), we measured ν(C≡N) IR bands of 30 para - and meta -substituted benzonitriles bearing C-, N-, and S-centered radicals. A linear scaling relationship was obtained between these experimental values and values obtained from DFT calculations. Using these computed values, two different Hammett constants, σ m , and σ p + , were determined for a series of C-, N-, O-, S-, Si-, and B-centered radicals. The differences between σm and σp+ values enable the separate evaluation of inductive and resonance effects in these open-shell substituents. The results suggest that there are three classes of radicals: one is electron withdrawing (σ m , σ p + > 0), one is electron donating (σm, σp+ < 0), and one is inductively withdrawing but resonance donating (σ m > 0, σ p + < 0). Our study represents a general approach to the analysis of the electronic properties of open-shell species and has potential applications in a wide range of molecular processes involving free radical intermediates.
Probing the mesoscopic size limit of quantum anomalous Hall insulators
The inelastic scattering length (L s ) is a length scale of fundamental importance in condensed matters due to the relationship between inelastic scattering and quantum dephasing. In quantum anomalous Hall (QAH) materials, the mesoscopic length scale L s plays an instrumental role in determining transport properties. Here we examine L s in three regimes of the QAH system with distinct transport behaviors: the QAH, quantum critical, and insulating regimes. Although the resistance changes by five orders of magnitude when tuning between these distinct electronic phases, scaling analyses indicate a universal L s among all regimes. Finally, mesoscopic scaled devices with sizes on the order of L s were fabricated, enabling the direct detection of the value of L s in QAH samples. Our results unveil the fundamental length scale that governs the transport behavior of QAH materials.
Quantized resistance revealed at the criticality of the quantum anomalous Hall phase transitions
In multilayered magnetic topological insulator structures, magnetization reversal processes can drive topological phase transitions between quantum anomalous Hall, axion insulator, and normal insulator states. Here we report an examination of the critical behavior of two such transitions: the quantum anomalous Hall to normal insulator (QAH-NI), and quantum anomalous Hall to axion insulator (QAH-AXI) transitions. By introducing a new analysis protocol wherein temperature dependent variations in the magnetic coercivity are accounted for, the critical behavior of the QAH-NI and QAH-AXI transitions are evaluated over a wide range of temperature and magnetic field. Despite the uniqueness of these different transitions, quantized longitudinal resistance and Hall conductance are observed at criticality in both cases. Furthermore, critical exponents were extracted for QAH-AXI transitions occurring at magnetization reversals of two different magnetic layers. The observation of consistent critical exponents and resistances in each case, independent of the magnetic layer details, demonstrates critical behaviors in quantum anomalous Hall transitions to be of electronic rather than magnetic origin. Our finding offers a new avenue for studies of phase transition and criticality in QAH insulators.
Simultaneous enhancement of multiple functional properties using evolution-informed protein design
Abstract A major challenge in protein design is to augment existing functional proteins with multiple property enhancements. Altering several properties likely necessitates numerous primary sequence changes, and novel methods are needed to accurately predict combinations of mutations that maintain or enhance function. Models of sequence co-variation (e.g., EVcouplings), which leverage extensive information about various protein properties and activities from homologous protein sequences, have proven effective for many applications including structure determination and mutation effect prediction. We apply EVcouplings to computationally design variants of the model protein TEM-1 β -lactamase. Nearly all the 14 experimentally characterized designs were functional, including one with 84 mutations from the nearest natural homolog. The designs also had large increases in thermostability, increased activity on multiple substrates, and nearly identical structure to the wild type enzyme. This study highlights the efficacy of evolutionary models in guiding large sequence alterations to generate functional diversity for protein design applications.
A study of real-world micrograph data quality and machine learning model robustness
Abstract Machine-learning (ML) techniques hold the potential of enabling efficient quantitative micrograph analysis, but the robustness of ML models with respect to real-world micrograph quality variations has not been carefully evaluated. We collected thousands of scanning electron microscopy (SEM) micrographs for molecular solid materials, in which image pixel intensities vary due to both the microstructure content and microscope instrument conditions. We then built ML models to predict the ultimate compressive strength (UCS) of consolidated molecular solids, by encoding micrographs with different image feature descriptors and training a random forest regressor, and by training an end-to-end deep-learning (DL) model. Results show that instrument-induced pixel intensity signals can affect ML model predictions in a consistently negative way. As a remedy, we explored intensity normalization techniques. It is seen that intensity normalization helps to improve micrograph data quality and ML model robustness, but microscope-induced intensity variations can be difficult to eliminate.
Abundant ammonia and nitrogen-rich soluble organic matter in samples from asteroid (101955) Bennu
Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all five nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH 3 -rich fluids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.
Dynamic nanodomains dictate macroscopic properties in lead halide perovskites
Lead halide perovskites have emerged as promising materials for solar energy conversion and X-ray detection owing to their remarkable optoelectronic properties. However, the microscopic origins of their superior performance remain unclear. Here we show that low-symmetry dynamic nanodomains present in the high-symmetry average cubic phases, whose characteristics are dictated by the A-site cation, govern the macroscopic behaviour. We combine X-ray diffuse scattering, inelastic neutron spectroscopy, hyperspectral photoluminescence microscopy and machine-learning-assisted molecular dynamics simulations to directly correlate local nanoscale dynamics with macroscopic optoelectronic response. Our approach reveals that methylammonium-based perovskites form densely packed, anisotropic dynamic nanodomains with out-of-phase octahedral tilting, whereas formamidinium-based systems develop sparse, isotropic, spherical nanodomains with in-phase tilting, even when crystallography reveals cubic symmetry on average. We demonstrate that these sparsely distributed isotropic nanodomains present in formamidinium-based systems reduce electronic dynamic disorder, resulting in a beneficial optoelectronic response, thereby enhancing the performance of formamidinium-based lead halide perovskite devices. By elucidating the influence of the A-site cation on local dynamic nanodomains, and consequently, on the macroscopic properties, we propose leveraging this relationship to engineer the optoelectronic response of these materials, propelling further advancements in perovskite-based photovoltaics, optoelectronics and X-ray imaging.
An expanded registry of candidate cis -regulatory elements
Mammalian genomes contain millions of regulatory elements that control the complex patterns of gene expression. Previously, the ENCODE consortium mapped biochemical signals across hundreds of cell types and tissues and integrated these data to develop a registry containing 0.9 million human and 300,000 mouse candidate cis-regulatory elements (cCREs) annotated with potential functions. Here we have expanded the registry to include 2.37 million human and 967,000 mouse cCREs, leveraging new ENCODE datasets and enhanced computational methods. This expanded registry covers hundreds of unique cell and tissue types, providing a comprehensive understanding of gene regulation. Functional characterization data from assays such as STARR-seq, massively parallel reporter assay, CRISPR perturbation and transgenic mouse assays have profiled more than 90% of human cCREs, revealing complex regulatory functions. We identified thousands of novel silencer cCREs and demonstrated their dual enhancer and silencer roles in different cellular contexts. Integrating the registry with other ENCODE annotations facilitates genetic variation interpretation and trait-associated gene identification, exemplified by the identification of KLF1 as a novel causal gene for red blood cell traits. This expanded registry is a valuable resource for studying the regulatory genome and its impact on health and disease.