Time Scale Research Articles

From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries.

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure-property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. This observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

On the utility of ultrafast MS1-only proteomics in drug target discovery studies based on thermal proteome profiling method.

Advances in high-throughput high-resolution mass spectrometry and the development of thermal proteome profiling approach (TPP) have made it possible to accelerate a drug target search. Since its introduction in 2014, TPP quickly became a method of choice in chemical proteomics for identifying drug-to-protein interactions on a proteome-wide scale and mapping the pathways of these interactions, thus further elucidating the unknown mechanisms of action of a drug under study. However, the current TPP implementations based on tandem mass spectrometry (MS/MS), associated with employing lengthy peptide separation protocols and expensive labeling techniques for sample multiplexing, limit the scaling of this approach for the ever growing variety of drug-to-proteomes. A variety of ultrafast proteomics methods have been developed in the last couple of years. Among them, DirectMS1 provides MS/MS-free quantitative proteome-wide analysis in 5-min time scale, thus opening the way for sample-hungry applications, such as TPP. In this work, we demonstrate the first implementation of the TPP approach using the ultrafast proteome-wide analysis based on DirectMS1. Using a drug topotecan, which is a known topoisomerase I (TOP1) inhibitor, the feasibility of the method for identifying drug targets at the whole proteome level was demonstrated for an ovarian cancer cell line.

Molecular Dynamics Simulation of Complex Reactivity with the Rapid Approach for Proton Transport and Other Reactions (RAPTOR) Software Package.

Simulating chemically reactive phenomena such as proton transport on nanosecond to microsecond and beyond time scales is a challenging task. Ab initio methods are unable to currently access these time scales routinely, and traditional molecular dynamics methods feature fixed bonding arrangements that cannot account for changes in the system's bonding topology. The Multiscale Reactive Molecular Dynamics (MS-RMD) method, as implemented in the Rapid Approach for Proton Transport and Other Reactions (RAPTOR) software package for the LAMMPS molecular dynamics code, offers a method to routinely sample longer time scale reactive simulation data with statistical precision. RAPTOR may also be interfaced with enhanced sampling methods to drive simulations toward the analysis of reactive rare events, and a number of collective variables (CVs) have been developed to facilitate this. Key advances to this methodology, including GPU acceleration efforts and novel CVs to model water wire formation are reviewed, along with recent applications of the method which demonstrate its versatility and robustness.

Parsimonious estimation of hourly surface ozone concentration across China during 2015–2020

Surface ozone is an important air pollutant detrimental to human health and vegetation productivity, particularly in China. However, high resolution surface ozone concentration data is still lacking, largely hindering accurate assessment of associated environmental impacts. Here, we collected hourly ground ozone observations (over 6 million records), remote sensing products, meteorological data, and social-economic information, and applied recurrent neural networks to map hourly surface ozone data (HrSOD) at a 0.1° × 0.1° resolution across China during 2015–2020. The coefficient of determination (R2) values in sample-based, site-based, and by-year cross-validations were 0.72, 0.65 and 0.71, respectively, with the root mean square error (RMSE) values being 11.71 ppb (mean = 30.89 ppb), 12.81 ppb (mean = 30.96 ppb) and 11.14 ppb (mean = 31.26 ppb). Moreover, it exhibits high spatiotemporal consistency with ground-level observations at different time scales (diurnal, seasonal, annual), and at various spatial levels (individual sites and regional scales). Meanwhile, the HrSOD provides critical information for fine-resolution assessment of surface ozone impacts on environmental and human benefits.

Sub-ppm Nanomechanical Absorption Spectroscopy of Silicon Nitride.

Material absorption is a key limitation in nanophotonic systems; however, its characterization is often obscured by scattering and diffraction. Here we show that nanomechanical frequency spectroscopy can be used to characterize material absorption at the parts per million level and use it to characterize the extinction coefficient κ of stoichiometric silicon nitride (Si3N4). Specifically, we track the frequency shift of a high-Q Si3N4 trampoline in response to laser photothermal heating and infer κ from a model including stress relaxation and both conductive and radiative heat transfer. A key insight is the presence of two thermalization time scales: rapid radiative cooling of the Si3N4 film and slow parasitic heating of the Si chip. We infer κ ∼ 0.1-1 ppm for Si3N4 in the 532-1550 nm wavelength range, matching bounds set by waveguide resonators. Our approach is applicable to diverse photonic materials and may offer new insights into their potential.

Non-Isochronal Behavior of Charge Transport at Liquid-Liquid and Liquid-Glass Transition in Aprotic Ionic Liquids.

A reversible, first-order transition separating two liquid phases of a single-component material is a fascinating yet poorly understood phenomenon. Here, we investigate the liquid-liquid transition (LLT) ability of two tetraalkylphosphonium ionic liquids (ILs), [P666,14]Cl and [P666,14][1,2,4-triazolide], using differential scanning calorimetry and dielectric spectroscopy. The latter technique also allowed us to study the LLT at elevated pressure. We found that cooling below 205 K transforms [P666,14]Cl and [P666,14][Trz] from one liquid state (liquid 1) to another (the self-assembled liquid 2), while the latter facilitates the charge transport decoupled from structural dynamics. In contrast to temperature, pressure was found to play an essential role in the self-organization of a liquid 2 phase, resulting in different time scales of charge transport for rapidly and slowly compressed samples. Furthermore, τσ(PLL) was found to be much shorter than τσ(TLL, P=atm), which constitutes the first example of non-isochronal behavior of charge transport at LLT. In turn, dielectric studies through the liquid-glass transition revealed the non-monotonic behavior of τσ at elevated pressure for [P666,14]Cl, while for [P666,14][Trz] τσ(Pg) was almost constant. These results highlight the diversity of liquid-liquid transition features within the class of phosphonium ionic liquids.

The Presence of Chaos in a Viscoelastic Harmonically Forced Von Mises Truss

Abstract This work investigates how viscoelasticity affects the dynamic behavior of a lumped-parameter model of a bistable von Mises truss. The system is controlled by a linear first-order equation and a second-order nonlinear Duffing equation with a quadratic nonlinearity that governs mechanical behavior. The second-order equation controls mechanical oscillations, while the linear first-order equation controls viscoelastic force evolution. Combined, the two equations form a third-order jerk equation that controls system dynamics. Viscoelasticity adds time scales and degrees-of-freedom to material behavior, distinguishing it from viscosity-only systems. Due to harmonic excitation, the system exhibits varied dynamic responses, from periodic to quasi-periodic to chaotic. We explore the dynamics of a harmonically forced von Mises truss with viscous damping to address this purpose. We demonstrate this system's rich dynamic behavior due to driving amplitude changes. This helps explain viscoelastic system behavior. A viscoelastic unit replaces the viscous damper, and we show that, although viscous damping merely changes how fast the trajectory decays to an attractor, viscoelasticity modifies both the energy landscape and the rate of decay. In a conventional linear solid model, three viscoelastic parameters control the system's behavior instead of one, as in pure viscous damping. This adds degrees-of-freedom that affect system dynamics. We present the parameter space for chaotic behavior and the shift from regular to irregular motion. Finally, Melnikov's criteria identify the regular-chaotic threshold. The system's viscous and elastic components affect the chaotic threshold amplitude

Interval prediction of crude oil spot price volatility: An improved hybrid model integrating decomposition strategy, IESN and ARIMA

Crude oil price volatility prediction are important for energy policymaking and investment risk avoidance, and have attracted a great deal of global attention. In recent years, although some studies have proposed methods for prediction crude oil price volatility, most of them are point prediction, which are difficult to provide richer reference information for managers. Therefore, an improved hybrid interval prediction model is proposed. The hybrid model combines data feature extraction and quantification techniques, fuzzy information granulation(FIG), improved echo state network (IESN), and autoregressive integrated moving average model (ARIMA). The hybrid model is able to accurately portray the different features present in the volatility of crude oil spot price. The features are quantified in order to merge similar feature components and improve the prediction effect. On this basis, IESN, which possesses strong nonlinear learning ability, is used to predict high-frequency sequences, and ARIMA, which has strong linear carving ability, is used to predict low-frequency sequences and residual terms. By “divide and conquer”, excellent prediction intervals are obtained. West Texas intermediate (WTI) crude oil spot and Brent crude oil spot are selected for analysis, and consider the influence of futures on interval construction. The effect of volatility intervals is validated from the pricing benchmark and time scale dimensions, respectively. The experimental results show that the proposed model has optimal performance in all scenarios. Take the performance of WTI on the daily scale as an example, its PICWC value is 0.8205. Compared with other benchmark models, it improves by 137.4504, 3.1118, 1.0506, and 0.4875, respectively. The proposed model provides a reliable new idea for crude oil spot volatility interval prediction.

Poroviscoelastic relaxations and rate-dependent adhesion in gelatin.

Hydrogels, polymeric networks swollen with water, exhibit time/rate-dependent adhesion due to their poroviscoleastic constitution. In this study, we conducted probe-tack experiments on gelatin and investigated the influence of dwelling times and unloading rates on pull-off forces and work of adhesion. We utilized in situ contact imaging to monitor separation kinematics and interfacial crack velocities. We found that the crack velocities scaled nonlinearly with the unloading rate, in a power law with an exponent of 0.8 and were independent of dwelling time. At maximum unloading rates corresponding to subsonic interfacial crack speeds, we observed an order of magnitude enhancement in the apparent work of adhesion. The enhancement of adhesion and the crack velocities were related by a power law with an exponent of 0.39. The maximum vertical extension during unloading, a measure of crack opening, exhibited linear correlation with the enhancement of adhesion. Both correlations were in line with the rate-dependent work of fracture modeled for viscoelastic solids (e.g., Persson and Brener model). We explored the links between dwelling times corresponding to varying degrees of poroelastic diffusion and the adhesion. We found 40% additional enhancement in adhesion at the highest unloading rate. This enhancement is due to the unbalanced osmotic pressure, also known as the suction effect. The influence of dwelling times on adhesion was negligible for the interfacial cracks propagating slower than the diffusive time scales. These results identify viscoelastic relaxations as the dominant mechanism governing the rate-dependent enhancement of adhesion, and hence pave the way for tuning rate-dependent adhesion in soft multiphasic materials.

Accounting for NOx emissions from biomass burning and urbanization doubles existing inventories over South, Southeast and East Asia

Rapid urbanization and broad use of biomass burning have led to important changes in NOx [sum of nitrogen dioxide and nitrous oxide] emissions across South, Southeast, and East Asia, frequently occurring on day-to-day time scales and over areas not identified by existing emissions databases. Here we compute NOx emissions using remotely sensed NO2 [nitrogen dioxide] and a model-free mass-conserving inverse method, resulting respectively in 61 kt d−1 and 40 kt d−1 from biomass burning in Northern and Southern Continental Southeast Asia, and 14.3 kt d−1 and 3.7 kt d−1 from urbanization in China and Eastern South Asia, a net increase more than double existing inventories. Three observationally based physical constraints consistent with theory are found which current chemical transport models cannot match: more NO2 per unit of NOx emissions, longer and more variable in-situ lifetime, and longer-range transport. This result provides quantitative support for mitigation efforts targeting specific events, processes, or geographies.

Causal Analysis Discovers an Enhanced Impact of Tropical Western Pacific on Indian Summer Monsoon Subseasonal Anomalies

AbstractExisting studies have shown changes in the impact of atmospheric teleconnections on Indian Summer Monsoon (ISM) at interannual time scales due to the changing background state. However, the exploration of potential changes at subseasonal time scales remains limited. In this study, we use a causal discovery method to find the tropical atmospheric drivers of ISM subseasonal anomalies, and quantify the causal effects of the drivers on ISM, as well as the changes in causal effects over the past 40 years. We find the impact of tropical western Pacific on ISM subseasonal anomalies has strengthened, while the ISM self‐feedback has weakened. Wavenumber‐frequency analysis shows that the Rossby wave energy over 15°N–30°N at periods of 10–20 days has increased over the past four decades, which offers a plausible explanation for the enhanced tropical atmospheric teleconnection between western Pacific and ISM at subseasonal time scales.

Digital Flow in a Pool Induced by a Vertical Jet

Turbulent water jets remain a critical study area, particularly the relation of the water flow with air entrainment and its role in energy dissipation at different hydraulic structures. Plunge pools, formed by the impact of jets on water cushions, play a pivotal role in energy dissipation. Understanding the complex flow dynamics within these pools is essential for designing efficient hydraulic structures. In this research, we present a comprehensive investigation of different numerical simulations, defining two-phase (air-water) in different ways, and them compare with experimental measurements. The primary objective is to analyze the pressure distribution at the bottom of a plunge pool induced by a vertical jet and understand the importance of accurately defining air-water flow in the dynamics of the jet into the pool. Our study bridges the gap between empirical data and computational modeling, shedding light on the intricate behavior of such flows with different method-based solvers: VOF, sub-grid, and multi-phase Euler. Various computational domains, mesh configurations, and analyses spanning different time periods, frequencies, and scales were considered.

Molecular Insights into the Effect of Cholesterol on the Binding of Bicarbonate Ions in Band 3 Protein.

Band 3, or anion exchanger 1 (AE1), is one of the indispensable transmembrane proteins involved in the effective respiratory process of the human body and is primarily responsible for the exchange of bicarbonate and chloride anions across the plasma membrane of erythrocyte. However, the molecular mechanism of ion transport of Band 3 is not completely understood, yet. In this work, we systematically investigate the key binding sites of bicarbonate ions in Band 3 and the impact of cholesterol (CHOL) in lipid bilayers on bicarbonate ion binding using all-atom molecular dynamics (MD) simulations. We examine the dynamics of interactions of bicarbonate ions with Band 3 in the microsecond time scale and calculate the binding free energy of the anion in Band 3. The results indicate that the residue R730 of Band 3 is the most probable binding site for bicarbonate ions. CHOL enhances the bicarbonate ion binding by influencing the conformational stability of Band 3 and compressing the volume of the Band 3 cavity. These findings provide some insights into the bicarbonate ion binding in Band 3 and are helpful for understanding the anion exchange of Band 3.

Exploring the geometry of the bifurcation sets in parameter space

By studying a nonlinear model by inspecting a p-dimensional parameter space through (p-1)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$(p-1)$$\\end{document}-dimensional cuts, one can detect changes that are only determined by the geometry of the manifolds that make up the bifurcation set. We refer to these changes as geometric bifurcations. They can be understood within the framework of the theory of singularities for differentiable mappings and, in particular, of the Morse Theory. Working with a three-dimensional parameter space, geometric bifurcations are illustrated in two models of neuron activity: the Hindmarsh–Rose and the FitzHugh–Nagumo systems. Both are fast-slow systems with a small parameter that controls the time scale of a slow variable. Geometric bifurcations are observed on slices corresponding to fixed values of this distinguished small parameter, but they should be of interest to anyone studying bifurcation diagrams in the context of nonlinear phenomena.

Linear, Electron-Rich Erbium Single-Molecule Magnet with Dibenzocyclooctatetraene Ligands.

Judicious design of ligand scaffolds to highly anisotropic lanthanide ions led to substantial advances in molecular spintronics and single-molecule magnetism. Erbium-based single-molecule magnets (SMMs) are rare, which is attributed to the prolate-shaped ErIII ion requiring an equatorial ligand field for enhancing its single-ion magnetic anisotropy. Here, we present an electron-rich mononuclear Er SMM, [K(crypt-222)][Er(dbCOT)2], 1 (where dbCOT = dibenzocyclooctatetraene), that was obtained from a salt metathesis reaction of ErCl3 and K2dbCOT. The dipotassium salt, K2dbCOT, was generated through a two-electron reduction of the bare dbCOT0 ligand employing potassium graphite and was crystallized from DME to give the new solvated complex, [K(DME)]2[dbCOT]n, 2. 1 was analyzed through crystallography, electrochemistry, spectroscopy, magnetometry, and CASSCF calculations. The structure of 1 consists of an anionic metallocene complex featuring a linear (180.0°) geometry with an ErIII ion sandwiched between dianionic dbCOT ligands and an outer-sphere K+ ion encapsulated in 2.2.2-cryptand. Two pronounced redox events at negative potentials allude to the formation of a trianionic erbocene complex, [Er(dbCOT)2]3-, on the electrochemical time scale. 1 shows slow magnetic relaxation with an effective spin-reversal barrier of Ueff = 114(2) cm-1, which is close in magnitude to the calculated energies of the first and second excited states of 96.9 and 109.13 cm-1, respectively. 1 exhibits waist-constricted hysteresis loops below 4 K and constitutes the first example of an erbocene-SMM bearing fused aromatic rings to the central COT ligand. Notably, 1 comprises the largest COT scaffold implemented in erbocene SMMs, yielding the most electron-rich homoleptic erbium metallocene SMM.

Determining the depth and rate of soil movement down the soil profile using an environmental tracer: a hillslope scale assessment

Context Soil materials can be delivered to depth from both in situ and ex situ materials. Here, we examine a hillslope in an agricultural environment that has been used for cropping and cattle grazing for over 150 years and a parallel area where cattle have been excluded for approximately 20 years. The exclusion area is a shelterbelt and also provides ecological services. Aims To quantify the depth and rate of down profile soil movement using the environmental tracer 137Cs at points along a hillslope profile. Methods 137Cs concentration is measured to bedrock at regular intervals both inside and outside a fenced of ecological services area pre-drought (2015) and post-drought (2021). In Australia. 137Cs is the by-product of nuclear weapons use and testing from1945 to 1972. Therefore, this places an age constraint on any labelled soil. Key results Results show that soil materials can move down the soil profile to reach bedrock at decadal time scales. An important finding is that materials from the surface can reach depths of up to 80 cm near the hillslope crest and up to 2.2 m at the base of the hillslope. Conclusions This demonstrates a relatively rapid translocation of surface material. Implications The method provides the ability to quantify the rapid movement of soil components and demonstrates the potential for deep sequestration of soil organic carbon. The results demonstrate the potential for soil amendments and agrochemicals to be rapidly transported to depth. The findings suggest that cattle exclusion has no impact on the movement of soil materials down the profile over the 20-year exclusion period.

Microscopic insights on liquid–vapor phase change phenomena of R1336mzz(Z) nanofilm through molecular dynamics simulations

The ever-growing advances in electronics pose a critical cooling challenge. Two-phase heat transfer technology, with effective heat removal and no extra energy consumption, is emerging as a potential solution for sustainable thermal management. However, questions regarding phase change mechanisms are seemingly not addressed yet due to the limitation in time and space scales. In this work, a series of molecular dynamics simulations are performed where the R1336mzz(Z) liquid film rests over a smooth copper substrate. The molecular system starts with a nanofilm thickness of 4–10 nm and then is subjected to non-equilibrium heating (350, 400, 450, and 500 K) to initiate liquid-to-vapor phase change. Depending on the impacts of film thickness and wall temperature, four distinctive phase change scenarios are identified, i.e., diffusive evaporation, pseudo-diffusive evaporation, explosive boiling, and stable explosive boiling. The characteristics of these phase change modes are explicated from the perspectives of molecular motion, vaporization rate, temperature evolution, heat flux, and interfacial resistance. The phase change mode has a strong dependence on two aspects: improving heat transfer to breakup potential barrier and slowing energy dissipation to support formation of bubble embryos. The insight may deliver better understandings of phase change mechanism and applications of liquid refrigerants.

Seasonal changes in ecosystem health and their spatial relationship with landscape structure in china's Loess plateau

Environmental managers have sought to optimize landscape structure to maintain regional ecosystem health (EH). However, we still lack a full understanding of the effects of changing landscape structure on EH, especially in terms of shorter time scales (e.g., monthly or seasonal scales) and spatial heterogeneity. To address this gap, this study used the vigor-organization-resilience-services (VORS) model to assess the annual and seasonal variation of EH in the Loess Plateau (LP) during 2000–2015, and then applied the geographically weighted regression (GWR) model to investigate the spatial effects of different aspects (i.e., landscape composition and configuration) of the landscape structure change on EH over time. Our results showed that the EH level in the LP from 2000 to 2015 displayed temporal non-stationarity at annual and seasonal scales, and a spatial pattern of decreasing from southeast to northwest. The effects of landscape structure on EH had obvious spatial and temporal heterogeneity, depending on the local landscape composition and configuration. In general, landscape configuration exerted a greater impact on EH than landscape composition apart from Shannon’s diversity index and percentage of forestland area, but the intensity and direction of the impact displayed higher temporally instability and therefore should receive more attention. Furthermore, regulation of the dominant patch size, landscape connectivity and forest spatial spacing is the optimal choice for regional ecosystem management. The results suggest that EH responses to changes in landscape structure in the LP vary by time and place, and that the integrating temporal variation and spatial characteristics can help decision-makers make precise spatial arrangements and temporal adjustments to keep the negative ecological impacts within reasonable limits.

Extension of Japan’s Prefectural Emission Accounting and Enrichment of Socioeconomic Data from 1990 to 2020

With the continuous increase in carbon dioxide emissions due to human activities and the resulting severe climate issues, there is global concern about energy conservation and emission reduction. However, detailed data on energy consumption and emissions at a fine-grained scale, particularly regarding spatial dimensions and sector-specific emissions, remains insufficient and in need of refinement and timely updates. In Japan, following the Fukushima nuclear disaster, there has been a significant shift from nuclear power generation to reliance on fossil fuels across various sectors, highlighting disparities in emissions data across different regions and industries. Our work extends the emissions time series for Japan’s 47 prefectures, incorporating their socioeconomic characteristics over a broader time frame and with a more detailed sectoral classification. The emissions inventory, covering the period from 1990 to 2020, is based on the consumption of the three main fossil fuels across 32 sectors, with emissions carefully allocated for regional power generation. This dataset, presented in a unified format, is expanded to include longer time scales and more detailed socioeconomic data. It is anticipated to offer crucial insights for establishing regional emission reduction targets and identifying sectoral priorities for decarbonization.

Decoupling Nucleation and Growth in Fast Crystallization of Phase Change Materials

AbstractDisentangling nucleation and growth in materials that crystallize on the nanosecond time scale is experimentally quite challenging since the relevant processes also take place on very small, i.e., sub‐micrometer length scales. Phase change materials are bad glass formers, which often crystallize rapidly. Here systematic changes in crystallization kinetics are shown in pseudo‐binary compounds of GeTe and Sb2Te3 and related solids subjected to short laser pulses. Upon systematic changes in stoichiometry, the speed of crystallization changes by three orders of magnitude concomitantly with pronounced changes in stochasticity. Resolving individual grains with electron backscatter diffraction (EBSD) permits to disentangle of the process of nucleation and growth. From these experiments, supported by multiphysics simulations of crystallization, it can be concluded that high crystallization speeds with small stochasticity characterize phase change materials with fast nucleation, while compounds that nucleate slowly crystallize much more stochastically.