Time-resolved Probe Research Articles

(Digital Presentation) Investigation of Electrochemical Cu Deposition on Nanoscale Sculptured Al Surfaces by FFT-Impedance Spectroscopy

Fast Fourier transform impedance spectroscopy (FFT-IS) is a well established technique to study in-situ e.g. the involved electrochemical dissolution and deposition phenomena at the electrolyte / substrate interface [1,2]. In contrast to conventional electrochemical impedance spectroscopy (EIS), FFT-IS allows for the simultaneous application of all probing frequencies at the same and thus highly time-resolved investigations of the ongoing electrochemical phenomena.FFT-IS has been employed to study the electrochemical deposition process of Cu on nano-scale-sculptured Al during the entire deposition process, since such a nanoscale-sculptured Al surface exhibits a high multitude of different-sized cubic undercut structures that must be enclosed and overgrown by Cu to generate a good mechanically interconnection between Al and Cu.The analysis of the IS data reveals that the deposition process can be modeled by an equivalent circuit consisting of a series resistance Rs and three Voigt-Kelvin elements, all connected in series to each other. The first one is a capacitor Cp1 and a resistor Rp1, followed by a Warburg element Zw and a resistor Rp2, and finally by another capacitor Cp3 and resistor Rp3 as last Voigt-Kelvin element, see Fig. 1.The time resolved analysis of the above described parameters reveals that three major processes are involved in the Cu deposition process that occur locally in series on the surface, but parallel in time. Based on the time evolution of these fit parameters the Cu deposition process can be sub-divided into three stages that were identified by investigating the nanoscale sculptured Al surface during Cu deposition at characteristic points of each stage by scanning electron microscopy. The knowledge and understanding of these processes allows tailoring and fine-tuning the Cu electrolyte and the deposition process itself.Fig. 1 Nyquist plot of recorded impedance data (boxes) and corresponding fit data (solid line) of the used equivalent circuit model[1] M. Leisner, J. Carstensen, and H. Föll, J. Electroanal. Chem. 615(2), 124 (2008). Figure 1

Time-resolved magneto-optical effects in the altermagnet candidate MnTe

α -MnTe is an antiferromagnetic semiconductor with above room temperature TN = 310 K, which is promising for spintronic applications. Recently, it was reported to be an altermagnet, containing bands with momentum-dependent spin splitting; time-resolved experimental probes of MnTe are, therefore, important both for understanding novel magnetic properties and potential device applications. We investigate ultrafast spin dynamics in epitaxial MnTe(001)/InP(111) thin films using pump-probe magneto-optical measurements in the Kerr configuration. At room temperature, we observe an oscillation mode at 55 GHz that does not appear at zero magnetic field. Combining field and polarization dependence, we identify this mode as a magnon, likely originating from inverse stimulated Raman scattering. Magnetic field-dependent oscillations persist up to at least 335 K, which could reflect coupling to known short-range magnetic order in MnTe above TN. Additionally, we observe two optical phonons at 3.6 and 4.2 THz, which broaden and redshift with increasing temperature.

In-situ imaging and time-resolved investigation of local pH in electrocatalytic CO2 reduction

Local pH near the catalyst surface exerts a substantial influence on both catalytic selectivity and activity in electrocatalytic CO2 reduction (CO2RR). While the investigation of local pH remains challenging in the aspect of in-situ imaging and monitoring. In this study, a novel lateral-type surface-enhanced Raman spectroscopy (L-SERS) system with a wide pH testing range from acidic to alkaline, is developed for the in-situ observation of local pH distributions with high spatial and temporal resolution during CO2RR. Excellent in-situ imaging of local pH near the catalyst surface is obtained, showing good consistency with simulation results. Besides, the gradual pH elevation and stabilization can be monitored via this time-resolved local pH investigation. This study presents a direct visualization of local pH distribution and variation at the Nernst layer during CO2RR, providing direct evidence in local pH for the feasibility of acidic electrolyte and offering theoretical guidance for optimizing CO2RR conditions.

A time-resolved investigation at multiple-length scales of the structure of liquid foam stabilized by albumins from pea

HypothesisThe structural details of foams made with pea albumins are affected by the pH of the initial solution and followed heat treatment. ExperimentsAn in situ, time-resolved investigation of foams prepared with pea albumins was conducted using small-angle neutron scattering (SANS) in combination with imaging and conductance measurements. Solutions were tested at pH three pH values (3, 4.5, and 8) before and after heating (90 °C for 1 and 5 min). FindingsThe characteristic structures present in the foam from the nano to the meso-scale differed during drainage depending on solution pH. Foams obtained at pH 3, had the largest bubble radius and thinnest plateau border, as well as the highest extent of liquid drainage. At pH 4.5, close to the isoelectric point of the proteins, foams displayed similar bubbles’ behavior to those at pH 8, but with the largest film thickness. In this case, the proteins were extensively aggregated. Heating of the solutions prior to foaming did not significantly affect the foam aging regardless of pH. The quantification of specific surface areas and film thickness over time without sample disruption shows to be a powerful approach to designing foam structures.

XUV-beamline for photoelectron imaging spectroscopy with shaped pulses.

We introduce an extreme ultraviolet (XUV)-beamline designed for the time-resolved investigation and coherent control of attosecond (as) electron dynamics in atoms and molecules by polarization-shaped as-laser pulses. Shaped as-pulses are generated through high-harmonic generation (HHG) of tailored white-light supercontinua (WLS) in noble gases. The interaction of shaped as-pulses with the sample is studied using velocity map imaging (VMI) techniques to achieve the differential detection of photoelectron wave packets. The instrument consists of the WLS-beamline, which includes a hollow-core fiber compressor and a home-built 4f polarization pulse shaper, and the high-vacuum XUV-beamline, which combines an HHG-stage and a versatile multi-experiment vacuum chamber equipped with a home-built VMI spectrometer. The VMI spectrometer allows the detection of photoelectron wave packets from both the multiphoton ionization (MPI) of atomic or molecular samples by the tailored WLS-pulses and the single-photon ionization (SPI) by the shaped XUV-pulses. To characterize the VMI spectrometer, we studied the MPI of xenon atoms by linearly polarized WLS pulses. To validate the interplay of these components, we conducted experiments on the SPI of xenon atoms with linearly polarized XUV-pulses. Our results include the reconstruction of the 3D photoelectron momentum distribution (PMD) and initial findings on the coherent control of the PMD by tuning the spectrum of the XUV-pulses with the spectral phase of the WLS. Our results demonstrate the performance of the entire instrument for HHG-based photoelectron imaging spectroscopy with prototypical shaped pulses. Perspectively, we will employ polarization-tailored WLS-pulses to generate polarization-shaped as-pulses.

Exploring the interaction between derivatives of urea with resorcinol-based acridinedione dyes by employing fluorescence methods and molecular docking approach

Akyl urea derivatives, either symmetrical or unsymmetrical in nature possessing a free N-H or N-alkyl moieties in the molecular framework of urea governs the excited state properties of acridinedione dye (ADR1) which is a resorcinol-based derivative. Fluorescence enhancement (FE) of ADR1 dye is observed on the addition of unsymmetrical urea derivatives, whereas a decrease in the fluorescence intensity resulted upon the addition of symmetrical urea derivatives. The nature of the urea derivatives controls the suppression of photoinduced electron transfer (PET) via space, which is the cause of the FE. FQ results from the donor and acceptor moieties of ADR1 dye promoting the PET process. Urea (U), symmetrical and unsymmetrical urea derivatives (except Tetramethyl urea (TMU)) results no significant shift of the localized excited (LE) state emission of ADR1 dye. Studies of the ADR1 dye’s fluorescence lifetime in the presence of urea compounds show a significant increase in lifetime. This phenomenon is explained by a significant difference in the hydrogen-bonding (HB) pattern, which causes variationin the microenvironment created by thesolute molecules in the aqueous phase. Both the hydrophobic effects of the alkyl group substituents in the urea molecular framework and the HB interactions between the solute and solvent influence the excited state features of ADR1 dye. Further, the role of urea derivatives and ADR1 dye (both are considered as competitive guest molecules) energetics and molecular interactions were studied in the presence of host molecule, Human Serum Albumin (HSA). The binding energy (BE) and several bimolecular interactions driven by urea derivatives in the presence of ADR1-HSA complex in comparison with that of urea derivatives-HSA complex were investigated by molecular docking (Mol.Doc) methodology. Incorporating theoretical research along withsteady state and time-resolved fluorescence investigations proved to be an effective method to evaluate the interactions of competing solutes comprising bothhydrophobic and HB functional groups.

A momentum-resolved view of polaron formation in materials

An ab-initio computational methodology for interrogating the phonon contribution to polaron formation in real materials is developed that can be directly compared to experiment. Using LiF as an example, we show that the recent ab-initio theory of Sio et al.1 makes predictions of the momentum- and branch dependent phonon amplitudes in polaron quasiparticles that are testable using ultrafast electron diffuse scattering (UEDS) and related techniques. The large electron polaron in LiF has UEDS signatures that are qualitatively similar to those expected from a simple isotropic strain field model, but the small hole polaron exhibits a profoundly anisotropic UEDS pattern that is in poor agreement with an isotropic strain field. We also show that these polaron diffuse scattering signatures are directly emblematic of the underlying polaron wavefunction. The combination of new time and momentum resolved experimental probes of nonequilibrium phonons with novel computational methods promises to complement the qualitative results obtained via model Hamiltonians with a first principles, material-specific quantitative understanding of polarons and their properties.

Electronic-Structure Interpretation: How Much Do We Understand Ce L3 XANES?

Historically, cerium has been attractive for pharmaceutical and industrial applications. The cerium atom has the unique ability to cycle between two chemical states (Ce(III) and Ce(IV)) and drastically adjust its electronic configuration: [Xe] 4f15d16s2 in response to a chemical reaction. Understanding how electrons drive chemical reactions is an important topic. The most direct way of probing the chemical and electronic structure of materials is by X-ray absorption spectroscopy (XAS) or X-ray absorption near-edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode. Such measurements at the Ce L3 edge have the advantage of a high penetration depth, enabling in-situ reaction studies in a time-resolved manner and investigation of material production or material performance under specific conditions. But how much do we understand Ce L3 XANES? This article provides an overview of the information that can be extracted from experimental Ce L3 XAS/XANES/HERFD data. A collection of XANES data recorded on various cerium systems in HERFD mode is presented here together with detailed discussions on data analysis and the current status of spectral interpretation, including electronic structure calculations.

Dual-Mode Fluorescent/Intelligent Lateral Flow Immunoassay Based on Machine Learning Algorithm for Ultrasensitive Analysis of Chloroacetamide Herbicides.

Given the harmful effect of pesticide residues, it is essential to develop portable and accurate biosensors for the analysis of pesticides in agricultural products. In this paper, we demonstrated a dual-mode fluorescent/intelligent (DM-f/DM-i) lateral flow immunoassay (LFIA) for chloroacetamide herbicides, which utilized horseradish peroxidase-IgG conjugated time-resolved fluorescent nanoparticle probes as both a signal label and amplification tool. With the newly developed LFIA in the DM-f mode, the limits of detection (LODs) were 0.08 ng/mL of acetochlor, 0.29 ng/mL of metolachlor, 0.51 ng/mL of Propisochlor, and 0.13 ng/mL of their mixture. In the DM-i mode, machine learning (ML) algorithms were used for image segmentation, feature extraction, and correlation analysis to obtain multivariate fitted equations, which had high reliability in the regression model with R2 of 0.95 in the range of 2 × 102-2 × 105 pg/mL. Importantly, the practical applicability was successfully validated by determining chloroacetamide herbicides in the corn sample with good recovery rates (85.4 to 109.3%) that correlate well with the regression model. The newly developed dual-mode LFIA with reduced detection time (12 min) holds great potential for pesticide monitoring in equipment-limited environments using a portable test strip reader and laboratory conditions using ML algorithms.

Microwave-assisted synthesis of novel pyrazolyl sulfones and their antimicrobial evaluation and time-resolved photoluminescence studies

This article reports an efficient and practical microwave-assisted MMPP-promoted synthesis of novel pyrazolyl sulfones from the corresponding 4-(alkyl/cycloalkylthio)-1H-pyrazoles. The reaction of 4-(alkyl/cycloalkylthio)-1H-pyrazoles with magnesium bis(monoperoxyphthalate)hexahydrate (MMPP) as an oxidizing agent afforded the corresponding 4-(alkyl/cycloalkylsulfonyl)-1,3-disubstituted-1H-pyrazoles in 85–95% yield. This method's benefits include its straightforward operation, simple workup, and use of an inexpensive, halogen-free MMPP oxidant that is easy to use and reasonably stable. All synthesized pyrazolyl sulfones were examined against bacterial and fungal strains, and notable antimicrobial activity was demonstrated by a few of the compounds. In order to investigate the prospect of connecting compounds with the highest yield and antimicrobial activity with their opto-electronic properties, time-resolved photoluminescence investigations for compounds 5a, 5b, and 5d were conducted. The tunable spectrum was observed in the micro-second time domain in all three cases, with fluorescent lifetime found higher in the compound having methyl group, intermediate with phenyl group, and lowest with the p-nitrophenyl group. Our procedures will encourage additional research into the valuable properties of pyrazolyl sulfones now that they are widely available with the structural complexity illustrated here.

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.

Time-resolved Spectroelectrochemical Investigation of Organic Mixed Conductors.

Organic mixed ionic and electronic conductors (OMIECs) are an emerging class of materials that have been applied for a wide range of electrochemical applications. Due to the complexity inherent to the ionic-electroniccoupling, understanding the underlying mechanisms involved in the OMIEC operation is an exciting and very lively research field. In this work, we highlight the use of time-resolved Vis-NIR spectroelectrochemistry tocharacterize these materials. We discuss an example, where we show that by combining this tool with spectraldecomposition, we are able to understand fundamental aspects of the doping in an OMIEC film. The methodswe present here can be generalized and used to characterize any electrochromic material.

Time-resolved spectroscopic investigation for the practical application of a photocatalytic air purifier

The photocatalytic efficiency for removing volatile organic compounds (VOCs) is significantly influenced by operational parameters like humidity and flow velocity, exhibiting notable and inconsistent fluctuations in both lab-scale and large-scale demonstrations. In this study, operando spectroscopy and isotope analysis were employed to investigate the correlation between humidity levels and degradation of gaseous acetaldehyde using TiO2 photocatalysts, aiming to demonstrate the scaling-up of photocatalytic air purifier. It was observed that rate constants for the mineralization of acetaldehyde rapidly decreased by 30% as relative humidity increased from 25% to 80% in the flow system (with an air velocity, v = 0.78 m/s). However, batch system showed smaller change with only a 10% reduction of the rate constant. Humidity fluctuations were more pronounced under high-speed conditions and were amplified in air purifier (v = 3.8 m/s). Time-resolved operando spectroscopy using an 13C isotope of acetaldehyde revealed that humidity’s distinct role in dark adsorption and photocatalytic reactions. Water was found to inhibit the formation of crotonaldehyde during aldol condensation reaction in dark condition. Moreover, water suppressed photocatalytic mineralization by inhibiting acetate oxidation to formate. These findings provide valuable insights for improving realistic air purification processes, underscoring the importance of identifying key intermediates and controlling humidity to enhance the selectivity of gaseous pollutant oxidation reactions.

Pump-Driven Opto-Magnetic Properties in Semiconducting Transition-Metal Dichalcogenides: An Analytical Model.

Single-layer transition-metal dichalcogenides provide an unique intrinsic entanglement between the spin/valley/orbital degrees of freedom and the polarization of scattered photons. This scenario gives rise to the well-assessed optical dichroism observed by using both steady and time-resolved probes. In this paper, we provide compact analytical modeling of the onset of a finite Faraday/Kerr optical rotation upon shining with circularly polarized light. We identify different optical features displaying optical rotation at different characteristic energies, and we describe in an analytical framework the time-dependence of their intensities as a consequence of the main spin-conserving and spin-flip processes.

Temperature field of non-Oberbeck–Boussinesq Rayleigh–Bénard convection in a low aspect ratio cell

A time-resolved experimental investigation was undertaken on the temperature evolution of Rayleigh–Bénard convection (RBC) in a slender convection cell with aspect ratio of Γ=0.1. Experiments were conducted for Rayleigh numbers of Ra=5.3×107, 7.6×107, and 9.5×107 and Prandtl number of Pr≈6 within the non-Oberbeck–Boussinesq (NOB) condition with a temperature difference variation in the range of 30 °C≤ΔT≤40 °C. Measurement of the temperature was by applying time-resolved two-color planar laser-induced fluorescence over the initial 2400 s. Experimental observations showed that the lateral confinement of the convection cell leads to the development of a single large-scale thermal plume instead of multiple plumes. Results showed that contrary to expectations, lateral confinement was found to be ineffective in suppressing temperature oscillations near thermal boundaries. Results also indicated that for Ra=5.3×107, 7.6×107, the temperature oscillations had a frequency of f≈0.028 Hz similar to the frequency of the oscillations in Oberbeck–Boussinesq (OB) RBC. For Ra=9.5×107, however, it was found that the frequency of the oscillations was much lower than the OB RBC with a relatively wide range of the oscillations in the vicinity of f≈0.006 Hz. It is also found that the lateral confinement and formation of singular high-energy thermal plumes leads to an increase in the nonsymmetrical temperature distribution of NOB RBC with a bimodal distribution of the temperature field, deviating significantly from the Gaussian distribution temperature field found in OB RBC.

Time-resolved spectral investigation of low-temperature plasma induced in gas mixtures by laser-produced plasma or nanosecond pulses of extreme ultraviolet radiation

Time-resolved spectral investigation of low-temperature plasma induced in gas mixtures by laser-produced plasma or nanosecond pulses of extreme ultraviolet radiation

Time-resolved investigations of a glow mode impulse dielectric barrier discharge in pure ammonia gas by means of E-FISH diagnostic

Time-resolved electric field strength measurements have been performed, using an electric-field induced second harmonic (E-FISH) diagnostic, in a nanosecond glow discharge of an impulse dielectric barrier discharge, in an ammonia gas environment. A temporal resolution of 2 ns and a spatial resolution estimated at 70 µm (given by laser waist) have been achieved. The comparative study of E-FISH measurements with and without a plasma discharge, operated at 4 kHz, reveal the presence of a persistent counter electric field, which is assumed to be caused by charge accumulation in between the AlN dielectrics used. Furthermore, by studying the influence of the applied voltage, the pressure, and the inter-dielectric distance, measurements seem to indicate the presence of charges remaining also in the post-discharge volume from the previous discharge to the next one.

Engineering Domain Variants in 0.7Pb(Mg1/3Nb2/3)-0.3PbTiO3 Single Crystals Using High-Frequency AC Poling.

Single crystals of (001)-oriented 0.7Pb(Mg1/3Nb2/3)-0.3PbTiO3 (PMN-30PT) with a composition near the morphotropic phase boundary have attracted considerable attention due to their superior dielectric and electromechanical performance. Recently, a new alternating current (electric field) poling approach used for the enhancement of dielectric and piezoelectric properties. However, the microscopic domain variants that govern the performance, especially under high-frequency alternating current (AC) voltages, remain largely unexplored. In this work, the domain microstructure under AC poling reveals the presence of four monoclinic (MA) domain variants using a suite of scanning probe microscopy methods, and X-ray diffraction (XRD) reciprocal space mapping is tuned. It is reported on the emergence of hierarchical fine domains - needle-shaped, and 109° domain walls under applied high-frequency AC poling. Time-resolved Kelvin probe force microscopy (KPFM) reveals the charge dynamics and relaxation behavior of these needle domains and walls. The findings provide new insight and guidance to the domain engineering by high-frequency AC poling for the development of advanced transducer technology.

Time-Resolved Ultraviolet Photodissociation Mass Spectrometry Probes the Mutation-Induced Alterations in Protein Stability and Unfolding Dynamics.

How mutations impact protein stability and structure dynamics is crucial for understanding the pathological process and rational drug design. Herein, we establish a time-resolved native mass spectrometry (TR-nMS) platform via a rapid-mixing capillary apparatus for monitoring the acid-initiated protein unfolding process. The molecular details in protein structure unfolding are further profiled by a 193 nm ultraviolet photodissociation (UVPD) analysis of the structure-informative photofragments. Compared with the wild-type dihydrofolate reductase (WT-DHFR), the M42T/H114R mutant (MT-DHFR) exhibits a significant stability decrease in TR-nMS characterization. UVPD comparisons of the unfolding intermediates and original DHFR forms indicate the special stabilization effect of cofactor NADPH on DHFR structure, and the M42T/H114R mutations lead to a significant decrease in NADPH-DHFR interactions, thus promoting the structure unfolding. Our study paves the way for probing the mutation-induced subtle changes in the stability and structure dynamics of drug targets.

Ultrafast Carrier Dynamics in Ba6Cr2S10 Modified by Toroidal Magnetic Phase Transition

Ba6Cr2S10 is a recently discovered magnetic material, in which the spins are aligned ferromagnetically in the ab-plane and anti-parallelly in a paired form along the c-axis. It is characterized as a quasi-one dimensional (1D) dimerized structure with a ferrotoroidic order, forming the simplest candidate toroidal magnetic (TM) order and exhibiting an anti-ferromagnetic-like transition at around 10 K. Time-resolved ultrafast dynamics investigation of the novel A–Cr–S (A: metal elements) family of quantum materials has rarely been reported. Here, we investigate the time-resolved pump-probe ultrafast dynamics of a Ba6Cr2S10 single crystal. A prominent change in the photo-excited carrier dynamics is observed at T c = 10 K, corresponding to the reported TM-paramagnetic phase transition. A potential unknown magnetic transition is also found at T * = 29 K. Our results provide new evidence for the TM magnetic transition in Ba6Cr2S10, and shed light on phase transitions in TM quantum materials.