Engineering topics
Publications and source records attributed to Hong, Liang.
Internal motions of folded proteins have been assumed to be ergodic, i.e. , that the dynamics of a single protein molecule averaged over a very long time resembles that of an ensemble.
Reference 1 states that we claimed that internal motions in single protein molecules exhibit ageing over 13 decades of time. In contrast, our primary conclusion, as expressed in the title, was that over these timescales the dynamics of single protein molecules is non-equilibrium and self-similar. Notwithstanding, we demonstrate in this reply that protein dynamics does indeed exhibit ageing according to the criteria of ref. 1.
The interaction between water and biomacromolecules is of fundamental interest in biophysics, biochemistry and physical chemistry.
Transition metal dichalcogenides (TMDCs) have garnered much attention recently due to their remarkable performance for different electrochemical systems. In this study, we report on the synthesis and catalysis of less studied TMDC nanoflakes (NFs) with a design space comprised of three transition metals (rhenium, ruthenium, and iridium) and three chalcogens (sulfur, selenium, and tellurium) for the oxygen reduction and evolution reactions (ORR and OER) in an aprotic hybrid electrolyte containing 0.1 M lithium bis(trifluoromethanesulfonypimide salt in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid and dimethyl sulfoxide. Our results indicate that among the tested catalysts, ReS2 exhibits the highest current density for both ORR and OER, beyond those of the state-of-the-art catalysts used in aprotic media with Li salts. We performed density functional calculations to provide a mechanistic understanding of the reactions in the ReS2 NFs/ionic liquid system. These novel bifunctional catalyst results could open a way for exploiting the unique properties of these materials in Li-O-2 batteries as well as other important electrochemical systems.
Abstract Antisite defects are a type of point defect ubiquitously present in intercalation compounds for energy storage applications. While they are often considered a deleterious feature, here we elucidate a mechanism of antisite defects enhancing lithium intercalation kinetics in LiFePO 4 by accelerating the FePO 4 → LiFePO 4 phase transformation. Although Fe Li antisites block Li movement along the [010] migration channels in LiFePO 4 , phase-field modeling reveals that their ability to enhance Li diffusion in other directions significantly increases the active surface area for Li intercalation in the surface-reaction-limited kinetic regime, which results in order-of-magnitude improvement in the phase transformation rate compared to defect-free particles. Antisite defects also promote a more uniform reaction flux on (010) surface and prevent the formation of current hotspots under galvanostatic (dis)charging conditions. We analyze the scaling relation between the phase boundary speed, Li diffusivity and particle dimensions and derive the criteria for the co-optimization of defect content and particle geometry. A surprising prediction is that (100)-oriented LiFePO 4 plates could potentially deliver better performance than (010)-oriented plates when the Li intercalation process is surface-reaction-limited. Our work suggests tailoring antisite defects as a general strategy to improve the rate performance of phase-changing battery compounds with strong diffusion anisotropy.
In contrast to molecular systems, which are defined with atomic precision, nanomaterials generally show some heterogeneity in size, shape, and composition. The sample inhomogeneity translates into a distribution of energy levels, band gaps, work functions, and other characteristics, which detrimentally affect practically every property of functional nanomaterials. Here, we introduce a novel synthetic strategy, colloidal atomic layer deposition (c-ALD) with stationary reactant phases, which largely circumvents the limitations of traditional colloidal syntheses of nano-heterostructures with atomic precision. This method allows for significant reduction of inhomogeneity in nanomaterials in complex nanostructures without compromising their structural perfection and enables the synthesis of epitaxial nano-heterostructures of unprecedented complexity. The improved synthetic control ultimately enables bandgap and strain engineering in colloidal nanomaterials with close to atomic accuracy. To demonstrate the power of the new c-ALD method, we synthesize a library of complex II–VI semiconductor nanoplatelet heterostructures. By combining spectroscopic and computational studies, we elucidate the subtle interplay between quantum confinement and strain effects on the optical properties of semiconductor nanostructures.
The surface properties of LiCoO 2 nanoplatelets, and their chemical modifications with Al 3+ , were studied using combined experimental and theoretical approaches. Our model shows that the electronic structures of several LiCoO 2 surface facets are significantly different from those of bulk LiCoO 2 , due to altered spin states of surface Co 3+ atoms. O K -edge X-ray absorption revealed a prominent splitting of the Co 3d -O 2p states, which is attributed to the presence of intermediate-state and/or high-spin-state Co 3+ . at the surface. In particular, the nonpolar (104) surface with intermediate-spin-state Co 3+ exhibits a strong two-dimensional character of splitting in these states, whereas the polar (001) surface with low-spin-state Co 3+ has a similar electronic structure to bulk LiCoO 2 . Here, partial substitution of Co 3+ by Al 3+ through the formation of core-shell architectures increases the ratio of low-spin-state Co3+, resulting in a distinct change in the intensity ratio of the split Co 3d -O 2p states, as revealed by spectroscopy.
The scattering of neutrons can be used to provide information on the structure and dynamics of biological systems on multiple length and time scales. Pursuant to a National Science Foundation-funded workshop in February 2018, recent developments in this field are reviewed here, as well as future prospects that can be expected given recent advances in sources, instrumentation and computational power and methods. Crystallography, solution scattering, dynamics, membranes, labeling and imaging are examined. For the extraction of maximum information, the incorporation of judicious specific deuterium labeling, the integration of several types of experiment, and interpretation using high-performance computer simulation models are often found to be particularly powerful.
Atomic-level structural characterization of flexible proteins, such as intrinsically disordered proteins and multi-domain proteins connected by flexible linkers, is challenging as they possess distinct conformations in physiological conditions. Significant efforts have been made to develop integrated approaches by combining small angle neutron/X-ray scattering experiments with molecular simulations to reveal the distinct atomic structures and the corresponding populations for these flexible proteins. One widely used method, the basis-set supported ensemble method, classifies the simulation-generated protein conformations into a set of structural basis and then derives the corresponding populations by fitting to the experimental data. This method makes an implicit assumption that protein conformations of similar structures have similar small angle scattering profiles.The present work demonstrates that, for various protein systems ranging from compact globular proteins and flexible multidomain proteins through to intrinsically disordered proteins, this method provides inaccurate assessment of the structural ensemble of the protein molecules due to the breakdown of the assumption made. To alleviate this problem, a two-fold-clustering method is developed to cluster the simulation-generated protein structures using information on both 3D structure and scattering profiles. As benchmarked by both simulation and experimental results, this new method yields much more accurate populations of structural basis of protein molecules.
Aquarius final product V5.0 has been released. The dataset includes close to four years of global radiometric measurements at L-band. The mission's objective was to monitor sea surface salinity, but other applications of its data over land and the cryosphere have been developed. For this reason, it is important to have accurate calibration over the full range of antenna temperatures from natural targets. It is also needed in order to combine Aquarius measurements with other L-band sensors. Aquarius calibration is strongly focused on the ocean. We present a research product which is part of the final release and aims at producing an accurate calibration from the low end (celestial sky) to the high end (land and ice) of the brightness temperature scale. We calibrate the Aquarius radiometers using measurements over the Sky and oceans and assess the new calibration using measurements over land.
Current performance and existing problems in SMAP radiometer L1B_TB version 3 data product are described. The post-launch calibration algorithm has been updated by calibrating the three calibration parameters (the equivalent noise temperature of the noise diode, the offset of the reference load, and the antenna gain) jointly by using the global ocean and CS with both 110o and 180o pitch maneuvers after the reflector emissivity is calibrated. The results show that both calibration drift during eclipse season and bias over CS are removed. The RMSDs of the calibration drift over both the global ocean and CS are less than 0.1 K, and the goals of the calibration algorithm upgrade are achieved for coming L1B_TB version 4 data release.
Dynamic neutron scattering directly probes motions in biological systems on femtosecond to microsecond timescales. When combined with molecular dynamics simulation and normal mode analysis, detailed descriptions of the forms and frequencies of motions can be derived. We examine vibrations in proteins, the temperature dependence of protein motions, and concepts describing the rich variety of motions detectable using neutrons in biological systems at physiological temperatures. In conclusion, new techniques for deriving information on collective motions using coherent scattering are also reviewed.
Ferroelectric materials have been extensively explored for applications in high-density nonvolatile memory devices because of their ferroelectric-ferroelastic domain-switching behavior under electric loading or mechanical stress. However, the existence of ferroelectric and ferroelastic backswitching would cause significant data loss, which affects the reliability of data storage. In this work, we apply in situ transmission electron microscopy and phase-field modeling to explore the unique ferroelastic domain-switching kinetics and the origin of this in relaxor-based Pb(Mg 1/3 Nb 2/3 )O 3 -33%PbTiO 3 single-crystal pillars under electrical and mechanical stimulations. Results showed that the electric-mechanical hysteresis loop shifted for relaxor-based single-crystal pillars because of the low energy levels of domains in the material and the constraint on the pillars, resulting in various mechanically reversible and irreversible domain-switching states. The phenomenon can potentially be used for advanced bit writing and reading in nonvolatile memories, which effectively overcomes the backswitching problem and broadens the types of ferroelectric materials for nonvolatile memory applications.
Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism and the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.
Interactions of water with cellulose are of both fundamental and technological importance. Here, we characterize the properties of water associated with cellulose using deuterium labeling, neutron scattering and molecular dynamics simulation. Quasi-elastic neutron scattering provided quantitative details about the dynamical relaxation processes that occur and was supported by structural characterization using small-angle neutron scattering and X-ray diffraction. We can unambiguously detect two populations of water associated with cellulose. The first is “non-freezing bound” water that gradually becomes mobile with increasing temperature and can be related to surface water. The second population is consistent with confined water that abruptly becomes mobile at ~260 K, and can be attributed to water that accumulates in the narrow spaces between the microfibrils. Quantitative analysis of the QENS data showed that, at 250 K, the water diffusion coefficient was 0.85 ± 0.04 × 10-10 m2sec-1 and increased to 1.77 ± 0.09 × 10-10 m2sec-1 at 265 K. MD simulations are in excellent agreement with the experiments and support the interpretation that water associated with cellulose exists in two dynamical populations. Our results provide clarity to previous work investigating the states of bound water and provide a new approach for probing water interactions with lignocellulose materials.
The electronic properties of epitaxial oxide thin films grown on compound semiconductors are largely determined by the interfacial atomic structure, as well as the thermodynamic conditions during synthesis. Ferroelectric polarization and Fermi-level pinning in SrTiO 3 films have been attributed to the presence of oxygen vacancies at the oxide/semiconductor interface. Here, we present scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy analyses of GaAs films grown on SrTiO 3 combined with first-principles calculations to determine the atomic and electronic structures of the SrTiO 3 /GaAs interfaces. In this work, an atomically abrupt SrO/As interface is observed and the interfacial SrO layer is found to be O-deficient. First-principles density functional theory (DFT) calculations show SrO/Ga and Sr/As interfaces are favorable under O-rich and O-poor conditions, respectively. The SrO/Ga interface is reconstructed via the formation of Ga-Ga dimers while the Sr/As interface is abrupt and consistent with the experiment. DFT calculations further reveal that intrinsic two-dimensional electron gas (2DEG) forms in both SrO/Ga and Sr/As interfaces, and the Fermi level is pinned to the localized 2DEG states. Interfacial O vacancies can enhance the 2DEG density while it is possible for Ga/As vacancies to unpin the Fermi level from the 2DEG states.