Time-resolved Analysis Research Articles

Time-resolved analysis of Ar metastable and electron populations in low-pressure misty plasma processes using optical emission spectroscopy

Misty plasmas have recently emerged as a promising tool for nanocomposite thin films deposition. However, aerosol-plasma interactions remain poorly documented, especially at low working pressure. In this work, optical emission spectroscopy is used to probe the temporal evolution of three fundamental plasma parameters during pulsed liquid injection in an inductively coupled argon plasma at low-pressure. Time-resolved values of metastable argon density, electron temperature, and electron density are determined from radiation trapping analysis and particle balance equations of selected argon 1s and 2p levels. Pulsed liquid injection is found to induce a sudden drop in metastable density and electron temperature, and an increase in electron density. These results are attributed to the lower ionization thresholds of the injected molecular species compared to the one of argon. In addition, upstream liquid temperature is found to affect the transitory kinetics for non-volatile solvents more than volatile ones, in accordance with a previously reported flash boiling atomization mechanism.

Unlocking Photocatalytic Activity of Acridinium Salts by Anion-Binding Co-Catalysis.

The in situ generation of active photoredox organic catalysts upon anion-binding co-catalysis by making use of the ionic nature of common photosensitizers is reported. Hence, the merge of anion-binding and photocatalysis permitted the modulation of the photocatalytic activity of simple acridinium halide salts, building an effective anion-binding - photoredox ion pair complex able to promote a variety of visible light driven transformations, such as anti-Markovnikov addition to olefins, Diels-Alder and the desilylative C-C bond forming reactions. Anion-binding studies, together with steady-state and time-resolved spectroscopy analysis, supported the postulated ion pair formation between the thiourea hydrogen-bond donor organocatalyst and the acridinium salt, which proved essential for unlocking the photocatalytic activity of the photosensitizer.

Reduced-Toxicity and Highly Luminescent Germanium-Lead Perovskites Enabled by Strain Reduction for Light-Emitting Diodes.

Germanium-lead (Ge-Pb) perovskites provide a promising solution for perovskite optoelectronic devices with reduced toxicity. However, Ge-Pb perovskite light-emitting diodes (PeLEDs) with >30 mol % Ge showed low emission efficiencies [Yang, D.; Zhang, G.; Lai, R.; Cheng, Y.; Lian, Y.; Rao, M.; Huo, D.; Lan, D.; Zhao, B.; Di, D. Germanium-Lead Perovskite Light-Emitting Diodes. Nat. Commun. 2021, 12 (1), 4295]. Here, we apply strain engineering to effectively improve the light emission efficiency and stability of Ge-Pb perovskite films and PeLEDs with 30 and 60 mol % Ge, through A-site modulation. The maximum external quantum efficiencies of the Ge-Pb PeLEDs with 30 and 60 mol % Ge are 8.5% and 3.0% at 3.32 mA cm-2 (∼922 cd m-2) and 0.53 mA cm-2 (∼60 cd m-2), respectively. Time-resolved transient absorption spectroscopy analysis of Ge-Pb perovskite films on different hole-transport layers shows that incorporating 30 mol % Ge into the perovskite with mixed A-site cations can effectively suppress trap-assisted recombination. Further analysis of their current density-voltage (J-V) curves reveals the efficiency loss mechanisms of Ge-Pb PeLEDs with high Ge fractions, indicating the possibility of further improvements.

RFX-mod2 diagnostic capability enhancements for the exploration of multi-magnetic-configurations

The RFX-mod2 device, the upgraded version of the previous RFX-mod with a modified magnetic boundary, is presently under realization and will start to be operated in 2025. Significant upgrades of the diagnostic capabilities have been proposed and are under development. These include a largely increased number of in-vessel magnetic and electrostatic sensors, a new fast reciprocating manipulator for the exploration of the edge plasma in a wide range of experimental conditions, the improved Thomson scattering and soft x-ray diagnostics system for a detailed determination of the behavior of the electron temperature profile, new dedicated systems for the space and time resolved analysis of x-ray spectra and neutron rate, a reflectometric diagnostic for real-time determination of plasma position, two diagnostics devoted to the imaging of light impurities and influxes behavior along with arrays of halo current sensors. These diagnostic upgrades will be accompanied by a significant effort to improve the control of the electron density and of the impurity influxes by means of proper treatment of plasma facing components with in-vessel fixed electrodes distributed over the first wall. The described advancements will allow a deeper understanding of physics phenomena in the wide variety of magnetic configurations, including the tokamak, the reversed-field pinch and the Ultra-low q, which can be produced in RFX-mod2 thanks to its flexibility and unique MHD control capabilities.

Exposing kinetic disparities between inflammasome readouts using time-resolved analysis

The NLRP3 inflammasome is an intracellular multiprotein complex described to be involved in both an effective host response to infectious agents and various diseases. Investigation into the NLRP3 inflammasome has been extensive in the past two decades, and often revolves around the analysis of a few specific readouts, including ASC-speck formation, caspase-1 cleavage or activation, and cleavage and release of IL-1β and/or IL-18. Quantification of these readouts is commonly undertaken as an endpoint analysis, where the presence of each positive outcome is assessed independently of the others. In this study, we apply time-resolved analysis of a human macrophage model (differentiated THP-1-ASC-GFP cells) to commonly accessible methods. This approach yields the additional quantifiable metrics time-resolved absolute change and acceleration, allowing comparisons between readouts. Using this methodological approach, we reveal (potential) discrepancies between inflammasome-related readouts that otherwise might go undiscovered. The study highlights the importance of time-resolved data in general and may be further extended as well as incorporated into other areas of research.

Detection of Simultaneous Quasiperiodic Oscillation Triplets in 4U 1728-34 and Constraining the Neutron Star Mass and Moment of Inertia

We report simultaneous detection of twin kHz and ∼40 Hz quasiperiodic oscillations (QPOs) in the time-resolved analysis of the AstroSat/LAXPC observation of the neutron star low-mass X-ray binary, 4U 1728-34. The frequencies of the multiple sets of triplets are correlated with each other and are consistent with their identification as the orbital, periastron precession, and twice the nodal precession frequencies. The observed relations, along with the known spin of the neutron star, put constraints on the mass and the ratio of the moment of inertia to the mass of the neutron star to be M⊙*=1.92±0.01 and I45/M⊙*=1.07±0.01 under the simplistic assumption that the metric is a Kerr one. We crudely estimate that the mass and moment of inertia values obtained may differ by about 1% and 5%, respectively, if a self-consistent metric is invoked. Using the Tolman–Oppenheimer–Volkoff equations for computing the moment of inertia of a neutron star in slow rotation approximation, having different equations of state, we find that the predicted values of neutron star parameters favor stiffer equations of state. We expect more stringent constraints would be obtained using a more detailed treatment, where the equation of state–dependent metric is used to compute the expected frequencies rather than the Kerr metric used here. The results provide insight into both the nature of these QPOs and the neutron star interior.

Endoplasmic reticulum protein ALTERED MERISTEM PROGRAM 1 negatively regulates senescence in Arabidopsis.

Plant senescence is a highly regulated developmental program crucial for nutrient reallocation and stress adaptation in response to developmental and environmental cues. Stress-induced and age-dependent natural senescence share both overlapping and distinct molecular responses and regulatory schemes. Previously, we have utilized a carbon-deprivation (C-deprivation) senescence assay using Arabidopsis (Arabidopsis thaliana) seedlings to investigate senescence regulation. Here we conducted a comprehensive time-resolved transcriptomic analysis of Arabidopsis wild type seedlings subjected to C-deprivation treatment at multiple time points, unveiling substantial temporal changes and distinct gene expression patterns. Moreover, we identified ALTERED MERISTEM PROGRAM 1 (AMP1), encoding an endoplasmic reticulum protein, as a potential regulator of senescence based on its expression profile. By characterizing loss-of-function alleles and overexpression lines of AMP1, we confirmed its role as a negative regulator of plant senescence. Genetic analyses further revealed a synergistic interaction between AMP1 and the autophagy pathway in regulating senescence. Additionally, we discovered a functional association between AMP1 and the endosome-localized ABNORMAL SHOOT3 (ABS3)-mediated senescence pathway and positioned key senescence-promoting transcription factors downstream of AMP1. Overall, our findings shed light on the molecular intricacies of transcriptome reprogramming during C-deprivation-induced senescence and the functional interplay among endomembrane compartments in controlling plant senescence.

Pitfalls in the Detection of Volatiles Associated with Heated Tobacco and e-Vapor Products When Using PTR-TOF-MS.

We investigated the applicability of proton transfer reaction-time-of-flight mass spectrometry (PTR-TOF-MS) for quantitative analysis of mixtures comprising glycerin, acetol, glycidol, acetaldehyde, acetone, and propylene glycol. While PTR-TOF-MS offers real-time simultaneous determination, the method selectivity is limited when analyzing compounds with identical elemental compositions or when labile compounds present in the mixture produce fragments that generate overlapping ions with other matrix components. In this study, we observed significant fragmentation of glycerin, acetol, glycidol, and propylene glycol during protonation via hydronium ions (H3O+). Nevertheless, specific ions generated by glycerin (m/z 93.055) and propylene glycol (m/z 77.060) enabled their selective detection. To thoroughly investigate the selectivity of the method, various mixtures containing both isotope-labeled and unlabeled compounds were utilized. The experimental findings demonstrated that when samples contained high levels of glycerin, it was not feasible to perform time-resolved analysis in H3O+ mode for acetaldehyde, acetol, and glycidol. To overcome the observed selectivity limitations associated with the H3O+ reagent ions, alternative ionization modes were investigated. The ammonium ion mode proved appropriate for analyzing propylene glycol (m/z 94.086) and acetone (m/z 76.076) mixtures. Concerning the nitric oxide mode, specific m/z were identified for acetaldehyde (m/z 43.018), acetone (m/z 88.039), glycidol (m/z 73.028), and propylene glycol (m/z 75.044). It was concluded that considering the presence of multiple product ions and the potential influence of other compounds, it is crucial to conduct a thorough selectivity assessment when employing PTR-TOF-MS as the sole method for analyzing compounds in complex matrices of unknown composition.

Microheterogeneity in the Kinetics and Sex-Specific Response to Type I IFN.

The response to type I IFNs involves the rapid induction of prototypical IFN signature genes (ISGs). It is not known whether the tightly controlled ISG expression observed at the cell population level correctly represents the coherent responses of individual cells or whether it masks some heterogeneity in gene modules and/or responding cells. We performed a time-resolved single-cell analysis of the first 3 h after invivo IFN stimulation in macrophages and CD4+ T and B lymphocytes from mice. All ISGs were generally induced in concert, with no clear cluster of faster- or slower-responding ISGs. Response kinetics differed between cell types: mostly homogeneous for macrophages, but with far more kinetic diversity among B and T lymphocytes, which included a distinct subset of nonresponsive cells. Velocity analysis confirmed the differences between macrophages in which the response progressed throughout the full 3 h, versus B and T lymphocytes in which it was rapidly curtailed by negative feedback and revealed differences in transcription rates between the lineages. In all cell types, female cells responded faster than their male counterparts. The ISG response thus seems to proceed as a homogeneous gene block, but with kinetics that vary between immune cell types and with sex differences that might underlie differential outcomes of viral infections.

Unveiling dissociation mechanisms and binding patterns in the UHRF1-DPPA3 complex via multi-replica molecular dynamics simulations.

Ubiquitin-like with PHD and RING finger domain containing protein 1 (UHRF1) is responsible for preserving the stability of genomic methylation through the recruitment of DNA methyltransferase 1 (DNMT1). However, the interaction between Developmental pluripotency associated 3 (DPPA3) and the pre-PHD-PHD (PPHD) domain of UHRF1 hinders the nuclear localization of UHRF1. This disruption has implications for potential cancer treatment strategies. Drugs that mimic the binding pattern between DPPA3 and PPHD could offer a promising approach to cancer treatment. Our study reveals that DPPA3 undergoes dissociation from the C-terminal through three different modes of helix unfolding. Furthermore, we have identified key residue pairs involved in this dissociation process and potential drug-targeting residues. These findings offer valuable insights into the dissociation mechanism of DPPA3 from PPHD and have the potential to inform the design of novel drugs targeting UHRF1 for cancer therapy. To comprehend the dissociation process and binding patterns of PPHD-DPPA3, we employed enhanced sampling techniques, including steered molecular dynamics (SMD) and conventional molecular dynamics (cMD). Additionally, we utilized self-organizing maps (SOM) and time-resolved force distribution analysis (TRFDA) methodologies. The Gromacs software was used for performing molecular dynamics simulations, and the AMBER FF14SB force field was applied to the protein.

AMPLITUDE EQUATIONS AND ORDER PARAMETERS OF HUMAN SARS-COV-2 INFECTIONS AND IMMUNE REACTIONS: A MODEL-BASED APPROACH

Several recent modeling studies have attempted to understand the human immune reaction to SARS-CoV-2 infections. Such a model-based understanding provides a sound basis for fighting COVID-19 on the level of individual patients. However, in this context, a worked-out nonlinear physics analysis providing insights into underlying amplitude equations and potential COVID-19 order parameters has not been conducted so far. In order to conduct such an analysis, a three-variable virus dynamics model is considered that can account for the human immune reaction to SARS-CoV-2 infections. The model amplitudes equations are derived and the relevant order parameter is determined. In line with theoretical reasoning, it is demonstrated that the order parameter and its amplitude determine the initial stage of SARS-CoV-2 infections, in general, and the initial dynamics of immune reactions, in particular. Explicitly, this finding is demonstrated for data from four COVID-19 patients. For those patients it is also demonstrated that the remnant of the order parameter determines the final disease decline phase. In this context, a time-resolved eigenvalue analysis is conducted that reveals that the transition from the initial stage to the decline stage which is associated with a switch of the leading eigenvalue from a positive to a negative value. It is argued that the immune reaction essentially contributes to this switch. From a medical-physics point of view, this observation suggests that the immune reaction of COVID-19 patients can stabilize the virus-free fixed point of affected sites.

Development of a Multiplexing Injector for Gas Chromatography for the Time-Resolved Analysis of Volatile Emissions from Lithium-Ion Batteries.

Multiplex sampling, so far mainly used as a tool for S/N ratio improvement in spectroscopic applications and separation techniques, has been investigated here for its potential suitability for time-resolved monitoring where chromatograms of transient signals are recorded at intervals much shorter than the chromatographic runtime. Different designs of multiplex sample introduction were developed and utilized to analyze lithium-ion battery degradation products under normal or abuse conditions to achieve fast and efficient sample introduction. After comprehensive optimization, measurements were performed on two different GC systems, with either barrier discharge ionization detection (BID) or mass spectrometric detection (MS). Three different injector designs were examined, and modifications in the pertinent hardware components and operational conditions used. The shortest achievable sample introduction time was 50 ms with an interval of 6 s. Relative standard deviations were lower than 4% and 10% for the intra- and inter-day repeatability, respectively. The sample introduction system and column head pressure had to be carefully controlled, as this parameter most critically affects the amount of sample introduced and, thus, detector response. The newly developed sample introduction system was successfully used to monitor volatile degradation products of lithium-ion batteries and demonstrated concentration changes over the course of time of the degradation products (e.g., fluoroethane, acetaldehyde and ethane), as well as for solvents from the battery electrolyte like ethyl carbonate.

Insights into the Dissociation Process and Binding Pattern of the BRCT7/8-PHF8 Complex.

DNA topoisomerase 2-binding protein 1 (Topbp1) plays a crucial role in activating the ataxia-telangiectasia mutated and rad3-related (ATR) complex to initiate DNA damage repair responses. For this process to occur, it is necessary for PHF8 to dissociate from Topbp1. Topbp1 binds to the acidic patch sequence (APS) of PHF8 through its C-terminal BRCT7/8 domain, and disrupting this interaction could be a promising strategy for cancer treatment. To investigate the dissociation process and binding pattern of BRCT7/8-PHF8, we employed enhanced sampling techniques, such as steered molecular dynamics (SMD) simulations and accelerated molecular dynamics (aMD) simulations, along with self-organizing maps (SOM) and time-resolved force distribution analysis (TRFDA) methodologies. Our results demonstrate that the dissociation of PHF8 from BRCT7/8 starts from the N-terminus, leading to the unfolding of the N-terminal helix. Additionally, we identified critical residues that play a pivotal role in this dissociation process. These findings provide valuable insights into the disassociation of PHF8 from BRCT7/8, which could potentially guide the development of novel drugs targeting Topbp1 for cancer therapy.

Polarization perspectives on Hercules X-1: further constraining the geometry

ABSTRACT We conduct a comprehensive analysis of the accreting X-ray pulsar, Hercules X-1, utilizing data from Imaging X-ray Polarimetry Explorer (IXPE) and Nuclear Spectroscopic Telescope Array. IXPE performed five observations of Her X-1, consisting of three in the Main-on state and two in the Short-on state. Our time-resolved analysis uncovers the linear correlations between the flux and polarization degree as well as the pulse fraction and polarization degree. Geometry parameters are rigorously constrained by fitting the phase-resolved modulations of Cyclotron Resonance Scattering Feature and polarization angle with a simple dipole model and Rotating Vector Model, respectively, yielding roughly consistent results. The changes of χp (the position angle of the pulsar’s spin axis on the plane of the sky) between different Main-on observations suggest the possible forced precession of the neutron star crust. Furthermore, a linear association between the energy of Cyclotron Resonance Scattering Feature and polarization angle implies the prevalence of a dominant dipole magnetic field, and their phase-resolved modulations likely arise from viewing angle effects.

1695: Time-resolved analysis of clinical dose metrics for HDR brachytherapy error detection

1695: Time-resolved analysis of clinical dose metrics for HDR brachytherapy error detection

Time-resolved analysis of CAR-T Cell induced apoptosis of low frequency target cells using an Image-enhanced flow cytometer was enabled by fluorescent protein compensation with BrightComp eBeads.

Time-resolved analysis of CAR-T Cell induced apoptosis of low frequency target cells using an Image-enhanced flow cytometer was enabled by fluorescent protein compensation with BrightComp eBeads.

Chemical screening by time-resolved X-ray scattering to discover allosteric probes

Drug discovery relies on efficient identification of small-molecule leads and their interactions with macromolecular targets. However, understanding how chemotypes impact mechanistically important conformational states often remains secondary among high-throughput discovery methods. Here, we present a conformational discovery pipeline integrating time-resolved, high-throughput small-angle X-ray scattering (TR-HT-SAXS) and classic fragment screening applied to allosteric states of the mitochondrial import oxidoreductase apoptosis-inducing factor (AIF). By monitoring oxidized and X-ray-reduced AIF states, TR-HT-SAXS leverages structure and kinetics to generate a multidimensional screening dataset that identifies fragment chemotypes allosterically stimulating AIF dimerization. Fragment-induced dimerization rates, quantified with time-resolved SAXS similarity analysis (kVR), capture structure–activity relationships (SAR) across the top-ranked 4-aminoquinoline chemotype. Crystallized AIF–aminoquinoline complexes validate TR-SAXS-guided SAR, supporting this conformational chemotype for optimization. AIF–aminoquinoline structures and mutational analysis reveal active site F482 as an underappreciated allosteric stabilizer of AIF dimerization. This conformational discovery pipeline illustrates TR-HT-SAXS as an effective technology for targeting chemical leads to important macromolecular states.

Competitive adsorption of gaseous acetic acid, ethanol and acetaldehyde onto wool powder

Natural resources are highly cost-effective adsorbents to reduce the indoor air pollution. However, there is a lack of understanding how the presence of several odor types affect their adsorption behavior. This study systematically investigates the adsorption selectivity and capacity of wool powder towards three typical odor types (acetic acid, ethanol and acetaldehyde) under single, binary and ternary systems through time-resolved spectral analysis and density functional theory (DFT) calculations. Wool powder showed different adsorption capacities for selected odor types in the single-component system. These findings were further manifested by DFT calculations to confirm the adsorption energy and surface adsorption sites between wool powder and odors. Acetic acid showed the highest competitivity among the tested odor types, followed by ethanol, which could be attributed to its high molecular weight and strong adsorption energy. This work provides new insights into adsorption mechanisms through adsorption energy analysis, promoting the application of natural proteaceous adsorbents.

Vacuum-Processed Propylene Urea Additive: A Novel Approach for Controlling the Growth of CH3NH3PbI3 Crystals in All Vacuum-Processed Perovskite Solar Cells.

In this study, we present a novel method for controlling the growth of perovskite crystals in the vacuum thermal evaporation process by utilizing a vacuum-processable additive, propylene urea (PU). By coevaporation of perovskite precursors with PU to form the perovskite layer, PU, acting as a Lewis base additive, retards the direct reaction between the perovskite precursors. This facilitates a larger domain size and reduced defect density. Following the removal of the residual additive, the perovskite layer, exhibiting improved crystallinity, demonstrates reduced charge recombination, as confirmed by a time-resolved microwave conductivity analysis. Consequently, there is a notable enhancement in open-circuit voltage and power conversion efficiency, increasing from 1.05 to 1.15 V and from 17.17 to 18.31%, respectively. The incorporation of a vacuum-processable and removable Lewis base additive into the fabrication of vacuum-processed perovskite solar cells offers new avenues for optimizing these devices.

Time-Resolved Local Loss Analysis of Single- and Two-Blade Pump Flow

Abstract A method for the evaluation of time-resolved entropy production in isothermal and incompressible flow is presented. It is applied as a postprocessing of the three-dimensional (3D) flow field obtained by time-resolved computational fluid dynamics (CFD) with scale adaptive turbulence modeling. Wall functions for direct and turbulent entropy production are presented for a cell-centered finite volume method, implemented in the open-source software OpenFOAM and validated on channel, asymmetric diffuser, and periodic hill flow. Single- and two-blade centrifugal pump flow is considered for a wide range of load conditions. Results are compared to experimental data. Time-averaged analysis shows essentially the same loss density distribution among pump components for both pumps, with the impeller and volute region contributing the most, especially in off-design conditions. For both pumps, the losses exhibit significant fluctuations due to impeller–volute interactions. The fluctuation magnitude of loss density is in the same range as flowrate fluctuations and much smaller than pressure fluctuation magnitude. For the two-blade pump (2BP), loss fluctuation magnitude is smaller than for the single-blade pump (1BP). Distinct loss mechanisms are identified for different load conditions. Upon blade passage, a promoted or attenuated volute tongue separation is imposed at part or overload, respectively. In between blade passages, a direct connection from pump inlet to the discharge leads to enhanced flowrate and loss density fluctuations. Future work aims at extending this analysis to stronger off-design conditions in multiblade pumps, where stochastic cycle fluctuations occur.