Time-resolved Measurements Research Articles

Sources and formation of fine particles and organic aerosols during autumn-winter period in the southern edge of northern China plain

The North China Plain (NCP) experienced significant improvements in air quality in 2018–2022. However, severe pollution episodes still occur frequently during the cold season. The limitations of highly time-resolved measurements hinder understanding the sources and formation mechanisms of pollution episodes, especially the role of organic aerosols (OA). Therefore, we used a Time-of-Flight Aerosol Chemical Speciation Monitor to characterize the aerosol chemical species, variation, and sources of OA during autumn and winter in Luohe, a city in the southern part of the NCP. The results showed that nitrates and organics were the main species of fine particles (PM2.5), accounting for an average of 38.4% and 29.6% of its total mass, respectively. Furthermore, the positive matrix factorization model analyzed the OA in PM2.5 and identified three primary OA and secondary OA related to photochemistry. Primary OA was the dominant contributor throughout the study period (55%), increasing from 50% during the non-heating period to 59% during the heating period. The contribution of photochemically generated oxidized OA remained high (41%) during heavy pollution episodes in the heating period, indicating strong photochemical production during winter. Additionally, most aerosol species and OA factors showed distinct diurnal variations, with lower concentrations during the day, suggesting the influence of the planetary boundary layer and primary emissions. By analyzing the chemical species features of five heavy particulate matter pollution episodes during the study period, we identified three main driving mechanisms for severe pollution events: photochemical processing, photochemical and aqueous-phase production, and local emissions.

A Technique for In-Situ Displacement and Strain Measurement with Laboratory-Scale X-Ray Computed Tomography

Abstract Purpose: Establish a technique for simultaneous interrupted volumetric imaging of internal structure and time-resolved full-field surface strain measurements during in-situ X-ray micro-computed tomography (XCT) experiments. This enables in-situ testing of stiff materials with large forces relative to the compliance of the in-situ load frame, which might exhibit localization (e.g., necking, compaction banding) and other inhomogeneous behaviors.Methods: The system utilizes a combination of in-situ XCT, 2D X-ray imaging, and particle tracking to conduct volumetric imaging of the internal structure of a specimen with interrupted loading and surface strain mapping during loading. Critically, prior to the laboratory-scale XCT experiments, specimens are speckled with a high-X-ray-contrast powder that is bonded the surface. During in-situ loading, the XCT system is programmed to capture sequential 2D X-ray images orthogonal to the speckled specimen surface. A single particle tracking (SPT) or digital image correlation (DIC) algorithm is used to measure full-field surface strain evolution throughout the time-sequence of images. At specified crosshead displacements, the motion and 2D image sequence is paused for volumetric XCT image collection. Results: We show example results on a micro-tensile demonstration specimen additive manufactured from Inconel 718 nickel-chrome alloy. Results include XCT volume reconstructions, crosshead-based engineering stress, and full-field strain maps. Conclusion: We demonstrate an in-situ technique to obtain surface strain evolution during laboratory-scale XCT testing and interrupted volumetric imaging. This allows closer investigation of, for example, the effect of micro-pores on the strain localization behavior of additive manufactured metal alloys. In addition to describing the method using a representative test piece, the dataset and code are published as open-source resources for the community. Graphical abstract

Imaging the dynamics of messenger RNA with a bright and stable green fluorescent RNA.

Fluorescent RNAs (FRs) provide an attractive approach to visualizing RNAs in live cells. Although the color palette of FRs has been greatly expanded recently, a green FR with high cellular brightness and photostability is still highly desired. Here we develop a fluorogenic RNA aptamer, termed Okra, that can bind and activate the fluorophore ligand ACE to emit bright green fluorescence. Okra has an order of magnitude enhanced cellular brightness than currently available green FRs, allowing the robust imaging of messenger RNA in both live bacterial and mammalian cells. We further demonstrate the usefulness of Okra for time-resolved measurements of ACTB mRNA trafficking to stress granules, as well as live-cell dual-color superresolution imaging of RNA in combination with Pepper620, revealing nonuniform and distinct distributions of different RNAs throughout the granules. The favorable properties of Okra make it a versatile tool for the study of RNA dynamics and subcellular localization.

Homogeneous distribution of highly dispersed Pt species over O and P co-doped g-C3N4 and its superior photocatalytic H2 evolution activity

In this study, we synthesized O and P co-doped graphitic C3N4 (OPCN) materials by a one-step calcination method and prepared Pt/OPCN photocatalysts for the photocatalytic H2 evolution reaction. Among the Pt/OPCN catalysts with various O and P contents, Pt/OPCN2 exhibited the highest H2 evolution rate of 2198 μmol·g−1 (AQE = 7.33 %), which was 1.65 times higher than that of Pt/CN (1330 μmol·g−1). Moreover, Pt/OPCN2 demonstrated excellent photocatalytic properties, such as suitable band gap (2.50 eV) for visible light and efficient charge separation of photoexcited electron–hole pairs, which was confirmed by ultraviolet-visible spectroscopy, electrochemical impedance spectroscopy, photoluminescence spectroscopy, and time-resolved photoluminescence measurements. Fundamentally, the Pt species effectively interacted with neighboring PO and CO functional groups that optimally located on defective OPCN2, resulting in a homogeneous formation of highly dispersed PtO evenly distributed over Pt/OPCN2, as confirmed by X-ray photoelectron spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, and density functional theory calculations. However, excessive O and P contents of OPCN3 damaged the morphological structure of g-C3N4, inducing a poor interaction between the Pt species and OPCN3 and forming isolated Pt nanoparticles, resulting in the low photocatalytic activity of Pt/OPCN3.

Optical-parametric-amplification-enhanced background-free spectroscopy.

Traditional absorption spectroscopy has a fundamental difficulty in resolving small absorbance from a strong background due to the instability of laser sources. Existing background-free methods in broadband vibrational spectroscopy help to alleviate this problem but face challenges in realizing either low extinction ratios or time-resolved field measurements. Here, we introduce optical-parametric-amplification-enhanced background-free spectroscopy, in which the excitation background is first suppressed by an interferometer, and then the free-induction decay that carries molecular signatures is selectively amplified. We show that this method can improve the limit of detection in linear interferometry by order(s) of magnitude without requiring lower extinction ratios or a time-resolved measurement, which can benefit sensing applications in detecting trace species.

Modification of Visible-Light-Responsive Pb2Ti2O5.4F1.2 with Metal Oxide Cocatalysts to Improve Photocatalytic O2 Evolution toward Z-Scheme Overall Water Splitting.

The development of a highly active photocatalyst for visible-light water splitting requires a high-quality semiconductor material and a cocatalyst, which promote both the migration of photogenerated charge carriers and surface redox reactions. In this work, a cocatalyst was loaded onto an oxyfluoride photocatalyst, Pb2Ti2O5.4F1.2, to improve the water oxidation activity. Among the metal oxides examined as cocatalysts, RuO2 was found to be the most suitable, and the O2 evolution activity depended on the preparation conditions for Ru/Pb2Ti2O5.4F1.2. The highest activity was obtained with RuCl3-impregnated Pb2Ti2O5.4F1.2 heated under a flow of H2 at 523 K. The H2-treated Ru/Pb2Ti2O5.4F1.2 showed an O2 evolution rate an order of magnitude higher than those for the analogues without the H2 treatment (e. g., RuO2/Pb2Ti2O5.4F1.2). Physicochemical analyses by X-ray absorption fine-structure spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and time-resolved microwave conductivity measurements indicated that the optimized photocatalyst contained partially reduced RuO2 species with a particle size of ~5 nm. These partially reduced species effectively trapped the photogenerated charge carriers and promoted the oxidation of water into O2. The optimized Ru/Pb2Ti2O5.4F1.2 could function as an O2-evolving photocatalyst in Z-scheme overall water splitting, in combination with an Ru-loaded, Rh-doped SrTiO3 photocatalyst.

Hydrophilic Photocrosslinkers as a Universal Solution to Endow Water Affinity to a Polymer Photocatalyst for an Enhanced Hydrogen Evolution Rate.

A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL-R) or ethylene glycol-based bridge chains (CL-TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365nm. When employing the hydrophilic CL-TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5-fold compared to that obtained using non-crosslinked F8BT photocatalysts, whereas CL-R-based photocatalysts yield HER rates comparable to those of non-crosslinked counterparts. Photophysical analyses including time-resolved photoluminescence and transient absorption measurements reveal that adding CL-TEG accelerates exciton separation, forming long-lived charge carriers. Additionally, the in-depth study using molecular dynamics simulations elucidates the dual role of CL-TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high-permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.

Structural intensity in thin plates and beams under transient and stationary forces using time-resolved, full-field optical slope measurements

Structural intensity, or structure-borne intensity or power flow, was introduced in the 1970s and implemented at that time using contact sensors like accelerometers. Point and contactless measurement methods removed added mass and sensor size constraints. Time-resolved and full-field vibration measurement techniques now open new perspectives for the estimation of structural intensity, but these prospects also come with many challenges. In this work, we study the applicability of optical deflectometry measurements to calculate the structural intensity in thin plates or beams under transient and stationary loadings. Since deflectometry directly provides slope fields, a slope formulation of structural intensity is proposed and evaluated. The effect of various parameters like frame rate (sampling frequency) and spatial resolution is studied from a numerical point of view on a simply-supported plate. Experimental results are then presented on a simply-supported plate and on a cantilever beam. Numerical and experimental results allow identifying the main challenges related to the implementation of structure intensity estimation using full-field and time-resolved data.

Boosting Excited-State Energy Transfer by Anchoring Dipole Orientation in Binary Thermally Activated Delayed Fluorescence/J-Aggregate Assemblies.

Förster resonance energy transfer (FRET) has been widely applied in fluorescence imaging, sensing and so on, while developing useful strategy of boosting FRET efficiency becomes a key issue that limits the application. Except optimizing spectral properties, promoting orientation factor (κ2) has been well discussed but rarely utilized for boosting FRET. Herein, we constructed binary nano-assembling of two thermally activated delayed fluorescence (TADF) emitters (2CzPN and DMAC-DPS) with J-type aggregate of cyanine dye (C8S4) as doping films by taking advantage of their electrostatic interactions. Time-resolved spectroscopic measurements indicated that 2CzPN/Cy-J films exhibit an order of magnitude higher kFRET than DMAC-DPS/Cy-J films. Further quantitative analysing on kFRET and kDET indicated higher orientation factor (κ2) in 2CzPN/Cy-J films play a key role for achieving fast kFRET, which was subsequently confirmed by anisotropic measurements. Corresponding DFT/TDDFT calculation revealed strong "two-point" electrostatic anchoring in 2CzPN/Cy-J films that is responsible for highly orientated transitions. We provide a new strategy for boosting FRET in nano-assemblies, which might be inspired for designing FRET-based devices of sensing, imaging and information encryption.

Photoinduced carrier transfer dynamics in a monolayer MoS2/PbS quantum dots heterostructure

Two-dimensional molybdenum disulfide (MoS2) has been proven to be a candidate in photodetectors, and MoS2/lead sulfide (PbS) quantum dots (QDs) heterostructure has been used to expand the optical response wavelength of MoS2. Time-resolved pump-probe transient absorption measurements are performed to clarify the carrier transfer dynamics in the MoS2/PbS heterostructure. By comparing the carrier dynamics in MoS2 and MoS2/PbS under different pump wavelengths, we found that the excited electrons in PbS QDs can transfer rapidly (<100 fs) to MoS2, inducing its optical response in the near-infrared region, although the pump light energy is lower than the bandgap of MoS2. Besides, interfacial excitons can be formed in the heterostructure, prolonging the lifetime of the excited carriers, which could be beneficial for the extraction of the carriers in devices.

A Coronin 1-Derived Peptide Inhibits Membrane Fusion by Modulating Membrane Organization and Dynamics.

Membrane fusion is considered the first step in the entry of enveloped viruses into the host cell. Several targeted strategies have been implemented to block viral entry by limiting the fusion protein to form a six-helix bundle, which is a prerequisite for fusion. Nonetheless, the development of broad-spectrum fusion inhibitors is essential to combat emerging and re-emerging viral infections. TG-23, a coronin 1, a tryptophan-aspartate-rich phagosomal protein-derived peptide, demonstrated inhibition of fusion between small unilamellar vesicles (SUVs) by modulating the membrane's physical properties. However, its inhibitory efficacy reduces with an increasing concentration of membrane cholesterol. The present work aims to develop a fusion inhibitor whose efficacy would be unaltered in the presence of membrane cholesterol. A stretch of the tryptophan-aspartic acid-containing peptide with a similar secondary structure and hydrophobicity profile of TG-23 from coronin 1 was synthesized, and its ability to inhibit SUV-SUV fusion with varying concentrations of membrane cholesterol was evaluated. Our results demonstrate that the GG-21 peptide inhibits fusion irrespective of the cholesterol content of the membrane. We have further evaluated the peptide-induced change in the membrane organization and dynamics utilizing arrays of steady-state and time-resolved fluorescence measurements and correlated these results with their effect on fusion. Interestingly, GG-21 displays inhibitory efficacy in a wide variety of lipid compositions despite having a secondary structure and physical properties similar to those of TG-23. Overall, our results advocate that the secondary structure and physical properties of the peptide may not be sufficient to predict its inhibitory efficacy.

Mechanically induced correlated errors on superconducting qubits with relaxation times exceeding 0.4 ms

Superconducting qubits are among the most advanced candidates for achieving fault-tolerant quantum computing. Despite recent significant advancements in the qubit lifetimes, the origin of the loss mechanism for state-of-the-art qubits is still subject to investigation. Furthermore, the successful implementation of quantum error correction requires negligible correlated errors between qubits. Here, we realize long-lived superconducting transmon qubits that exhibit fluctuating lifetimes, averaging 0.2 ms and exceeding 0.4 ms – corresponding to quality factors above 5 million and 10 million, respectively. We then investigate their dominant error mechanism. By introducing novel time-resolved error measurements that are synchronized with the operation of the pulse tube cooler in a dilution refrigerator, we find that mechanical vibrations from the pulse tube induce nonequilibrium dynamics in highly coherent qubits, leading to their correlated bit-flip errors. Our findings not only deepen our understanding of the qubit error mechanisms but also provide valuable insights into potential error-mitigation strategies for achieving fault tolerance by decoupling superconducting qubits from their mechanical environments.

Transonic Compressor Darmstadt Open Test Case: Experimental Investigation of Stator Secondary Flows and Hub Leakage

Abstract The future trend of clean sky aviation has led to a smaller core engine, resulting in highly loaded stages with increased relative tip gaps and leakage flows, which causes a reinforced influence of secondary flow phenomena. This article experimentally investigates the secondary flow effects in the 3D-optimized shrouded stator of the TUDa-GLR-OpenStage, representative of a transonic high-pressure compressor front stage, and its susceptibility to typical hub leakage flows. The impact of stator hub leakage on efficiency and total pressure ratio is investigated for several operating speeds, from subsonic to nominal transonic operating conditions. Steady five-hole probe and time-resolved virtual multi-hole probe measurements at different operating conditions at nominal speed are conducted to investigate the underlying loss mechanisms. The leakage mass flow is determined using the measured pressure difference within the fin seal. Steady results show that the optimized 3D stator effectively suppresses the hub corner separation compared to the predecessor 2D stator, but its performance is further limited by a near-tip separation. With the increased stator hub leakage (at a leakage-to-main flow ratio of about 0.4%), the compressor isentropic efficiency generally drops (by about −0.5%) at the full operating range due to an enhanced hub corner separation effect. However, the increased leakage also helps alleviate the tip-corner separation when operating near stall, leading to a smaller efficiency penalty under these conditions. Unsteady results reveal the sensitivity of transient compressor performance to the passing rotor wake, but limited interaction between this phenomenon and the increased leakage is observed. These findings provide insight into the stator hub leakage-related penalties on the compressor aerodynamics efficiency.

Transient reflectance of silicon carbide during laser-induced phase separation

Laser irradiation can induce local modulations of functional material properties, such as a decreased resistivity or a variation in reflectance. Recent studies investigated the laser-induced phase separation of 4 H-SiC into carbon and silicon on top of regrown SiC to customize its electrical conductivity for the application in electronic devices. To understand the physical processes leading to the laser-induced phase separation, time-resolved pump-probe measurements represent a suitable tool. This study advances the state of the art by characterizing the transient reflectance changes in 4 H-SiC upon irradiation by spatially resolved pump-probe reflectometry. Since the laser heating alters the reflectance of the sample, the spatially resolved measurement enables to observe the heat conduction from the irradiated to the non-irradiated areas, which sustains for several milliseconds. Numerical simulations of the temperature evolution reveal a restricted one-dimensional heat conduction into depth due to the broad lateral extent of the irradiated area. The associated sustained increased temperature within the irradiated area most certainly abets the feasibility of the phase separation. These findings offer practical insights for optimizing the applied laser parameters to tailor the material properties via phase separation.

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene derivative

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene (fDAE) derivative were investigated by time-resolved absorption and fluorescence spectroscopies. Prescreening with quantum chemical calculation predicted that a derivative with methylthienyl groups (mt-fDAE) in the closed-ring isomer has a two-photon absorption cross-section larger than 1000 GM, which was experimentally verified by Z-scan measurements and excitation power dependence in transient absorption. Comparison of transient absorption spectra under one-photon and simultaneous two-photon excitation conditions revealed that the closed-ring isomer of mt-fDAE populated into higher excited states deactivates following three pathways on a timescale of ca. 200 fs: (i) the cycloreversion reaction more efficient than that by the one-photon process, (ii) internal conversion into the S1 state, and (iii) relaxation into a lower state (S1’ state) different from the S1 state. Time-resolved fluorescence measurements demonstrated that this S1’ state is relaxed to the S1 state with the large emission probability. These findings obtained in the present work contribute to extension of the ON–OFF switching capability of fDAE to the biological window and application to super-resolution fluorescence imaging in a two-photon manner.Graphical

Computationally-efficient linear scheme for overlap time-gating spatial frequency domain diffuse optical tomography using an analytical diffusion model.

Time-domain (TD) spatial frequency domain (SFD) diffuse optical tomography (DOT) potentially enables laminar tomography of both the absorption and scattering coefficients. Its full time-resolved-data scheme is expected to enhance performances of the image reconstruction but poses heavy computational costs and also susceptible signal-to-noise ratio (SNR) limits, as compared to the featured-data one. We herein propose a computationally-efficient linear scheme of TD-SFD-DOT, where an analytical solution to the TD phasor diffusion equation for semi-infinite geometry is derived and used to formulate the Jacobian matrices with regard to overlap time-gating data of the time-resolved measurement for improved SNR and reduced redundancy. For better contrasting the absorption and scattering and widely adapted to practically-available resources, we develop an algebraic-reconstruction-technique-based two-step linear inversion procedure with support of a balanced memory-speed strategy and multi-core parallel computation. Both simulations and phantom experiments are performed to validate the effectiveness of the proposed TD-SFD-DOT method and show an achieved tomographic reconstruction at a relative depth resolution of ∼4 mm.

Dominant n-type conduction and fast photoresponse in BP/MoS2 heterostructures

In recent years, van der Waals heterojunctions between two-dimensional (2D) materials have garnered significant attention for their unique electronic and optoelectronic properties and have opened avenues for innovative device architectures and applications. Among them, the heterojunction formed by black phosphorus (BP) and molybdenum disulfide (MoS2) stands out as a promising candidate for advanced optoelectronic devices. This study unravels the interplay between BP, MoS2, and Cr contacts to explain the electrical behavior of a BP/MoS2 heterojunction showing rectifying behavior with dominant n-type conduction, and a high ON/OFF current ratio around 104 at ± 20 V. The higher unexpected current observed when applying a negative bias to either MoS2 or BP side is elucidated by an energy band model incorporating a type II heterojunction at the BP/MoS2 interface with Cr forming a Schottky contact with MoS2 and an ohmic contact with BP. The BP/MoS2 heterojunction shows pronounced photoresponse, linearly dependent on the incident laser power, with a responsivity of 100 µA/W under white light at 50 µW incident power. Time-resolved photocurrent measurements reveal a relatively fast response with characteristic rise times less than 200 ms. This work demonstrates that BP/MoS2 van der Waals heterojunctions have unique electrical and photoresponse characteristics that are promising for advanced optoelectronic applications.

Measurements of time resolution of the RD50-MPW2 DMAPS prototype using TCT and 90Sr

Results in this paper present an in-depth study of time resolution for active pixels of the RD50-MPW2 prototype CMOS particle detector. Measurement techniques employed include Backside- and Edge-TCT configurations, in addition to electrons from a 90Sr source. A sample irradiated to 5 · 1014 neq/cm2 was used to study the effect of radiation damage. Timing performance was evaluated for the entire pixel matrix and with positional sensitivity within individual pixels as a function of the deposited charge. Time resolution obtained with TCT is seen to be uniform throughout the pixel's central region with approx. 220 ps at 12 ke- of deposited charge, degrading at the edges and lower values of deposited charge. 90Sr measurements show a slightly worse time resolution as a result of delayed events coming from the peripheral areas of the pixel.

Time-resolved measurement of optical emission line profiles from electron cyclotron resonance ion source plasma

Optical emission spectroscopy provides a non-invasive method to probe the properties of hot and highly charged magnetically confined plasmas. The optical emission line profiles enable, for example, to identify the different species and characterize the relative population densities and temperatures of the ions and neutrals forming the plasma. The feasibility of this approach has been demonstrated at the University of Jyväskylä accelerator laboratory by measuring the light emitted by Electron Cyclotron Resonance Ion Source (ECRIS) plasma with a high-resolution spectrometer setup POSSU (Plasma Optical SpectroScopy Unit). In these previous studies, the emission line profiles were measured by scanning the desired wavelength range by rotating the diffraction grating of the spectrometer. This process is slow compared to many interesting plasma phenomena, thus limiting the applicability of the setup. Recently, POSSU has been upgraded by changing the light sensor from a photomultiplier tube to a position-sensitive imaging sensor. As a result, it is possible to measure simultaneously a 1 - 2 nm wavelength range, with a spectral resolution in the order of picometers, without moving the grating. This enables a time-resolved study of the optical emission line profiles. By turning the grating, the measured wavelength region can be chosen between 370 nm and 870 nm, which covers the visible light spectrum. The time-evolution of optical emission line profiles emitted from the JYFL 14 GHz ECRIS plasma, during shifting plasma conditions induced by changing the gas balance, has been measured to demonstrate this new capability. The time-evolution of temperatures and emission intensities of selected ion species, correlated with extracted ion beam currents, are presented.

Direct Observation of a Roaming Intermediate and Its Dynamics.

Chemical reactions are often characterized by their transition state, which defines the critical geometry the molecule must pass through to move from reactants to products. Roaming provides an alternative picture, where in a dissociation reaction, the bond breaking is frustrated and a loosely bound intermediate is formed. Following bond breaking, the two partners are seen to roam around each other at distances of several Ångstroms, forming a loosely bound, and structurally ill-defined, intermediate that can subsequently lead to reactive or unreactive collisions. Here, we present a direct and time-resolved experimental measurement of roaming. By measuring the photoelectron spectrum of UV-excited acetaldehyde with a femtosecond extreme ultraviolet pulse, we captured spectral signatures of all of the key reactive structures, including that of the roaming intermediate. This provided a direct experimental measurement of the roaming process and allowed us to identify the time scales by which the roaming intermediate is formed and removed and the electronic potential surfaces upon which roaming proceeds.