Ultrafast Techniques Research Articles

Ultrafast Microwave-Assisted Synthesis of Porous NiCo Layered Double Hydroxide Nanospheres for High-Performance Supercapacitors.

Currently, new clean energy storage technology must be effective, affordable, and ecologically friendly so as to meet the diverse and sustainable needs of the energy supply. In this work, NiCo-LDH containing intercalated EG was successfully prepared within 210 s using an ultrafast microwave radiation technique. Subsequently, a series of characterization and systematic electrochemical tests were conducted to analyze the composition, structure, and energy storage mechanism of the NiCo-LDH material. The Ni:Co ratio of 5:5 results in the highest capacitance value of 2156 F/g at 1 A/g and an outstanding rate performance of 86.8% capacity retention rate at 10 A/g. The results demonstrated that the unique porous structure of NiCo-LDH and large layer spacing were conducive to more electrochemical reactions. Additionally, an electrochemical test was carried out on the NiCo-LDH as a hybrid supercapacitor electrode material, with NiCo-LDH-5:5 serving as the positive electrode and activated carbon as the negative electrode, the asymmetric supercapacitor can achieve a maximum energy density of 82.5 Wh kg-1 and power density of 8000 W kg-1. The NiCo-LDH-5:5//AC hybrid supercapacitors own 81.5% cycle stability and 100% coulombic efficiency after 6000 cycles at 10 A/g.

Time distribution of stimulated transition probabilities

In recent years, an increasing number of experimental results have been published for a wide variety of systems in which high-precision, ultra-fast, and ultra-short laser pulses techniques have been used to study time-resolved dynamical processes. In the absence of a theoretical prediction of the time distribution of the transition probabilities, the lifetimes τ are generally extracted by fitting the decay time with an exponential, bi-exponential or three-exponential function. In fitting the data, the short-time behavior is generally neglected. The purpose of this study is to show that an explicit formula for the time distribution of the transition probability can be determined rigorously using time-dependent perturbation theory. A formula that perfectly fits an important subset of the experimental results from t = 0 to t=∞ . We show that by following a route different from the usual procedure for deriving transition amplitudes and Einstein coefficients in time-dependent perturbation theory, one ends up with a time-dependent factor, that is, a temporal distribution function of the transition probabilities, and for the Einstein coefficients. The time distribution reported here looks in the time domain similar to the Planck distribution in the frequency domain. In fact, the behavior of the time distribution, with a maximum at 2τln⁡2 , and with τ playing the role of temperature, resembles the behavior of the Planck frequency distribution. We present several examples to demonstrate that the theoretical formula allows for easier fitting of the experimental results reported in the literature. We also show that the time distribution explains the difference in resonance heights between the experimental and theoretical blue laser spectra.

Excited States in Single-Stranded and i-Motif DNA with Silver Ions.

We have studied the excited states and structural properties for the complexes of cytosine (dC)10 chains with silver ions (Ag+) in a wide range of the Ag+ to DNA ratio (r) and pH conditions using circular dichroism, steady-state absorption, and fluorescence spectroscopy along with the ultrafast fluorescence upconversion technique. We also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in some models of the cytosine-Ag+ complexes. We show that (dC)10 chains in the presence of silver ions form a duplex stabilized by C-Ag+-C bonds. It is also shown that the i-motif structure formed by (dC)10 chains is destabilized in the presence of Ag+ ions. The excited-state properties in the studied complexes depend on the amount of binding ions and the binding sites, which is supported by the calculations. In particular, new low-lying excited states appear when the second Ag+ ion interacts with the O atom of cytosine in the C-Ag+-C pairs. A similar picture is observed in the case when one Ag+ ion interacts with one cytosine via the N7 atom.

Single-Shot Intensity- and Phase-Sensitive Compressive Sensing-Based Coherent Modulation Ultrafast Imaging.

Ultrafast imaging can capture the dynamic scenes with a nanosecond and even femtosecond temporal resolution. Complementarily, phase imaging can provide the morphology, refractive index, or thickness information that intensity imaging cannot represent. Therefore, it is important to realize the simultaneous ultrafast intensity and phase imaging for achieving as much information as possible in the detection of ultrafast dynamic scenes. Here, we report a single-shot intensity- and phase-sensitive compressive sensing-based coherent modulation ultrafast imaging technique, shortened as CS-CMUI, which integrates coherent modulation imaging, compressive imaging, and streak imaging. We theoretically demonstrate through numerical simulations that CS-CMUI can obtain both the intensity and phase information of the dynamic scenes with ultrahigh fidelity. Furthermore, we experimentally build a CS-CMUI system and successfully measure the intensity and phase evolution of a multimode Q-switched laser pulse and the dynamical behavior of laser ablation on an indium tin oxide thin film. It is anticipated that CS-CMUI enables a profound comprehension of ultrafast phenomena and promotes the advancement of various practical applications, which will have substantial impact on fundamental and applied sciences.

A Novel Perspective on Enhancing Photocatalytic Performance through the Synergistic Effect of Nd Single Atoms and Heterostructures.

There are few reports on lanthanide single atom modified catalysts, as the role of the 4f levels in photocatalysis is difficult to explain clearly. Here, the synergistic effect of 4f levels of Nd and heterostructures is studied by combining steady-state, transient, and ultrafast spectral analysis techniques with DFT theoretical calculations based on the construction of Nd single atom modified black phosphorus/g-C3N4 (BP/CN) heterojunctions. As expected, the generation rates of CO and CH4 of the optimized heterostructure are 7.44 and 6.85 times higher than those of CN, and 8.43 and 9.65 times higher than those of BP, respectively. The Nd single atoms can not only cause surface reconstruction and regulate the active sites of BP, but also accelerate charge separation and transfer, further suppressing the recombination of electron-hole pairs. The electrons can transfer from g-C3N4:Nd to BP:Nd, with a transfer time of ≈11.4ps, while the radiation recombination time of electron-hole pairs of g-C3N4 is ≈26.13 µs, indicating that the construction of heterojunctions promotes charge transfer. The 2P1/2/2G9/2/4G7/2/2H11/2/4F7/2→4I9/2 emissions from Nd3+ can also be absorbed by heterostructures, which improves the utilization of light. The energy change of the key rate measurement step CO2 *→COOH* decreases through Nd single atom modification.

Influence of Hot Carrier Cooling and Band‐Filling Effect on Linewidth of Perovskite Microlasers

AbstractIn semiconductor‐based microlasers, the generated excited carriers can affect both the optical absorption coefficient and refractive index, influencing the lasing behavior and device performance. In this study, the lasing behavior of individual MAPbBr3 microrods pumped by femtosecond laser pulses is investigated using an ultrafast optical Kerr gating technique. By analyzing the spectral and temporal evolution of the lasing behavior, it is found that the band‐filling (BF) effect can cause a significant change in the refractive index of the material, which results in an unfavorable red‐shift and broadening of the resonant modes, deteriorating the laser linewidth and quality factor. The hot carrier cooling process can provide a buffer for alteration of the energy level occupation state, resulting in a small transient refractive index change and slight red‐shift. These results offer insights into the lasing behavior driven by photogenerated carrier dynamics and provide an optimization strategy for semiconductor‐based microlasers.

Unraveling the conundrum of electronic leakage in protonic ceramic cells: Operation-specific insights and rational design strategies

Electronic conduction through proton-conducting electrolytes significantly impairs the efficiency of protonic ceramic cells (PCCs). In this study, we explore the electron and ion mixed transport properties of four common protonic ceramics, BaZr0.8Y0.2O3-δ (BZY82), BaZr0.7Ce0.2Y0.1O3-δ (BZCY721), BaZr04Ce0.4Y0.1Yb0.1O3-δ (BZCYYb4411), and BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb1711). It marks the first instance of investigating these properties under operation-specific scenarios: fuel side of electrolysis cell, air side of electrolysis cell, fuel side of fuel cell, and air side of the fuel cell. BZCYYb1711 exhibits the highest ionic conductivity, but two to three times higher electronic leakage when exposed to oxygen-containing environments than the others. BZY82 exhibits approximately two times higher electronic leakage in a hydrogen-containing environment. BZCY721 demonstrates excellent ion transport numbers (∼0.95) across these four operating conditions. BZCYYb4411 behaves quite similarly to BZCY721. The most challenging operating environment for all candidates is the air side of fuel cell mode. This mode leads to a high initial electronic leakage, followed by a significant increase with polarization. The probable cause for this behavior is a H2-free, polarization-induced reduction that leads to the formation of VO•. The electron small polaron associated with VO• is released by the electrical field due to the Poole-Frenkel effect. ZnO and NiO sintering aids are found to be detrimental to the ionic conductivity of the electrolytes. In particular, NiO substantially lowers the ion transport number. The correlation of the operation-specific electronic leakage to full cells is discussed. It is suggested that a rational PCC design should synergistically couple BZCYYb1711 at fuel side with BZCY4411 at air side to deliver a well-balanced performance and faradaic efficiency simultaneously, and the high temperature sintering process with a NiO fuel electrode should be shortened or replaced by ultra-fast sintering techniques or using a fuel electrode scaffold-infiltration fabrication strategy.

Coherent phonon and unconventional carriers in the magnetic kagome metal Fe3Sn2

Temperature- and fluence-dependent carrier dynamics of the magnetic kagome metal Fe3Sn2 were studied using the ultrafast optical pump-probe technique. Two carrier relaxation processes and a laser-induced coherent optical phonon were observed. We ascribe the shorter relaxation (~1 ps) to hot electrons transferring their energy to the crystal lattice via electron–phonon scattering. The second relaxation (~30 ps), on the other hand, cannot be explained as a conventional process, and we attributed it to the unconventional (localized) carriers in the material. The observed coherent oscillation is assigned to be a totally symmetric A1g optical phonon dominated by Sn displacements out of the kagome planes and possesses a prominently large amplitude, on the order of 10−3, comparable to the maximum of the reflectivity change (ΔR/R). This amplitude is similar to what has been observed for coherent phonons in charge-density-wave (CDW) systems, although no signs of such instability were hitherto reported in Fe3Sn2. Our results suggest an unexpected connection between Fe3Sn2 and kagome metals with CDW instabilities and a strong interplay between phonon and electron dynamics in this compound.

Leveraging Intermolecular Charge Transfer for High-Speed Optical Wireless Communication.

Intermolecular charge transfer (CT) complexes have emerged as versatile platforms with customizable optical properties that play a pivotal role in achieving tunable photoresponsive materials. In this study, we introduce an innovative approach for enhancing the modulation bandwidth and net data rates in optical wireless communications (OWCs) by manipulating combinations of monomeric molecules within intermolecular CT complexes. Concurrently, we extensively investigate the intermolecular charge transfer mechanism through diverse steady-state and ultrafast time-resolved spectral techniques in the mid-infrared range complemented by theoretical calculations using density functional theory. These intermolecular CT complexes empower precise control over the -3 dB bandwidth and net data rates in OWC applications. The resulting color converters exhibit promising performance, achieving a net data rate of ∼100 Mb/s, outperforming conventional materials commonly used in the manufacture of OWC devices. This research underscores the substantial potential of engineering intermolecular charge transfer complexes as an ongoing progression and commercialization within the OWC. This carries profound implications for future initiatives in high-speed and secure data transmission, paving the way for promising endeavors in this area.

Capturing the Chirality of Photoexcited States with Ultrafast Circular Dichroism.

Chiral molecules exist in two forms, called enantiomers, which are mirror images of each other but non-superimposable. Even though enantiomers share most chemical and physical properties, they may differ greatly in their (bio-)chemical activities, which turns chirality into a key design feature for (bio-)chemical function. In this spirit, the incorporation of chiral structures into photochemical systems has emerged as a powerful strategy to control their functions. For example, uni-directional molecular motors, chiral photocatalysts, and chiral metal nanostructures permit new levels of stereocontrol over mechanical motion, energy transfer, and electric charge-carriers on the nanoscale. However, the direct characterization of the underlying chiral photoexcited states remains a formidable experimental challenge - especially in the native solution phase of many photochemical processes. Crucially, this requires analytical techniques that combine a high chiral sensitivity in solution with ultrafast time resolution to capture the excited state dynamics. This brief perspective article presents recent progress in the development of ultrafast chiral spectroscopy techniques that address this challenge.

Measuring Protein-Ligand Binding by Hyperpolarized Ultrafast NMR.

Protein-ligand interactions can be detected by observing changes in the transverse relaxation rates of the ligand upon binding. The ultrafast NMR technique, which correlates the chemical shift with the transverse relaxation rate, allows for the simultaneous acquisition of R2 for carbon spins at different positions. In combination with dissolution dynamic nuclear polarization (D-DNP), where the signal intensity is enhanced by thousands of times, the R2 values of several carbon signals from unlabeled benzylamine are observable within a single scan. The hyperpolarized ultrafast chemical shift-R2 correlated experiment separates chemical shift encoding from the readout phase in the NMR pulse sequence, which allows it to beat the fundamental limit on the spectral resolution otherwise imposed by the sampling theorem. Applications enabled by the ability to measure multiple relaxation rates in a single scan include the study of structural properties of protein-ligand interactions.

Quantifying Dielectric Material Charge Trapping and De-Trapping Ability Via Ultra-Fast Charge Self-Injection Technique.

Recently, utilizing the air breakdown effect in the charge excitation strategy proves as an efficient charge injection technique to increase the surface charge density of dielectric polymers for triboelectric nanogenerators (TENGs). However, quantitative characterization of the ability of dielectric polymers to trap reverse charges and the effect on the startup time of secondary self-charge excitation (SSCE) are essential for extensive applications. Here, an ultra-fast charge self-injection technique based on a self-charge excitation strategy is proposed, and a standard method to quantify the charge trapping and de-trapping abilities of 23 traditional tribo-materials is introduced. Further, the relationship among the distribution of dielectric intrinsic deep, shallow trap states, and transportation of trapped charges is systematically analyzed in this article. It shows that the de-trapping rate of charges directly determines the reactivation and failure of SSCE. Last, independent of TENG contact efficiency, an ultra-high charge density of 2.67 mC m-2 and an ultra-fast startup time of SSCE are obtained using a 15µm poly(vinylidene fluoride-trifluoroethylene) film, breaking the historical record for material modification. As a standard for material selection, this work quantifies the charge trapping and de-trapping ability of the triboelectric dielectric series and provides insights for understanding the charge transport in dielectrics.

Highly efficient upconversion photodynamic performance of rare-earth-coupled dual-photosensitizers: ultrafast experiments and excited-state calculations

Abstract Upconversion photodynamic therapy (UC-PDT), which integrates upconversion nanoparticles (UCNPs) with photosensitizers (PSs), presents a promising advancement in the field of phototherapy. However, despite the extensive studies focused on the design and synthesis of UCNPs, there is a paucity of systematic research on the mechanisms underlying the synergistic upconversion photodynamic effects. Here we have synthesized upconversion core@dotted-shell nanoparticles (CDSNPs) and covalently tethered them with two distinct PSs, thereby constructing a dual-PS UC-PDT system with high synergistic photodynamic performance. To unravel the mechanism underlying the synergism, we employed a combination of quantum mechanical calculations and ultrafast time-resolved spectroscopy techniques. The results indicate that rare earth oxides play a pivotal role in enhancing the intersystem crossing processes of PSs through modulating their excited electronic states. Additionally, Förster resonance energy transfer between two distinct PSs contributes to the amplification of triplet state populations, thus further enhancing the photodynamic effect. In vitro experiments demonstrate that the prepared CDSNPs based dual-PS system exhibits excellent biocompatibility with normal cells and exceptional synergistic photodynamic efficacy against tumor cells upon near-infrared excitation. This research contributes theoretical insights into the design and application of multi-photosensitizer UC-PDT systems, laying the groundwork for more efficient preclinical implementations in the future.

Two-dimensional electronic spectroscopy from first principles

The recent development of multidimensional ultrafast spectroscopy techniques calls for the introduction of computational schemes that allow for the simulation of such experiments and the interpretation of the corresponding results from a microscopic point of view. In this work, we present a general and efficient first-principles scheme to compute two-dimensional electronic spectroscopy maps based on real-time time-dependent density-functional theory. The interface of this approach with the Ehrenfest scheme for molecular dynamics enables the inclusion of vibronic effects in the calculations based on a classical treatment of the nuclei. The computational complexity of the simulations is reduced by the application of numerical advances such as branching techniques, undersampling, and a novel reduced phase cycling scheme, applicable for systems with inversion symmetry. We demonstrate the effectiveness of this method by applying it to prototypical molecules such as benzene, pyridine, and pyrene. We discuss the role of the approximations that inevitably enter the adopted theoretical framework and set the stage for further extensions of the proposed method to more realistic systems.

Unveiling Carrier Relaxation Mechanism in Protonated/Deprotonated Carbon Dots and Their Solvent Effects via Ultrafast Spectroscopy.

The intricate nature of the surface structure of carbon dots (CDs) hinders a comprehensive understanding of their emission behavior. In this study, we employ two types of CDs created through acid-alkali treatments, one with surface protonation and the other with surface deprotonation, with the objective of investigating the impact of these surface modifications on carrier behavior using ultrafast spectroscopy techniques. TEM, XRD, FTIR and Raman spectra demonstrate the CDs' structure, featuring graphitic core and abundant surface functional groups. XPS confirms the successful surface modifications of CDs via protonation and deprotonation. Ultrafast transient absorption (TA) spectroscopy reveals that deprotonation modification may decelerate the relaxation process, thereby increasing the visible PL quantum yields (PLQY). Conversely, protonation may accelerate the relaxation process due to the induced low-energy absorption band, resulting in self-absorption and reduced PLQY. Furthermore, TA analysis of CDs in mixed solvents with different proportions of ethanol shows the beneficial effect of ethanol in decelerating the relaxation process, leading to an increased PLQY of 33.7 % for deprotonated CDs and 22.1 % for protonated CDs. This study illuminates the intricate relationship between surface deprotonation/protonation modifications and carrier behavior in CDs, offering a potential avenue for the design of high-brightness CDs for diverse applications.

Four-Dimensional Flow Echocardiography: Blood Speckle Tracking in Congenital Heart Disease: How to Apply, How to Interpret, What Is Feasible, and What Is Missing Still.

Blood speckle tracking echocardiography (BSTE) is a new, promising 4D flow ultrafast non-focal plane imaging technique. The aim of the present investigation is to provide a review and update on potentialities and application of BSTE in children with congenital heart disease (CHD) and acquired heart disease. A literature search was performed within the National Library of Medicine using the keywords "echocardiography", "BST", and "children". The search was refined by adding the keywords "ultrafast imaging", "CHD", and "4D flow". Fifteen studies were finally included. Our analysis outlined how BSTE is highly feasible, fast, and easy for visualization of normal/abnormal flow patterns in healthy children and in those with CHD. BSTE allows for visualization and basic 2D measures of normal/abnormal vortices forming the ventricles and in the main vessel. Left ventricular vortex characteristics and aortic flow patterns have been described both in healthy children and in those with CHD. Complex analysis (e.g., energy loss, vorticity, and vector complexity) are also highly feasible with BSTE, but software is currently available only for research. Furthermore, current technology allows for BSTE only in neonates and low-weight children (e.g., <40 kg). In summary, the feasibility and potentialities of BSTE as a complementary diagnostic tool in children have been proved; however, its systemic use is hampered by the lack of (i) accessible tools for complex quantification and for acquisition at all ages/weight, (ii) data on the diagnostic/prognostic significance of BSTE, and (iii) consensus/recommendation papers indicating when and how BSTE should be employed.

Ultrastrong and High Thermal Insulating Porous High-Entropy Ceramics up to 2000°C.

High mechanical load-carrying capability and thermal insulating performance are crucial to thermal-insulation materials under extreme conditions. However, these features are often difficult to achieve simultaneously in conventional porous ceramics. Here, for the first time, it is reported a multiscale structure design and fast fabrication of 9-cation porous high-entropy diboride ceramics via an ultrafast high-temperature synthesis technique that can lead to exceptional mechanical load-bearing capability and high thermal insulation performance. With the construction of multiscale structures involving ultrafine pores at the microscale, high-quality interfaces between building blocks at the nanoscale, and severe lattice distortion at the atomic scale, the materials with an ≈50% porosity exhibit an ultrahigh compressive strength of up to ≈337MPa at room temperature and a thermal conductivity as low as ≈0.76W m-1 K-1. More importantly, they demonstrate exceptional thermal stability, with merely ≈2.4% volume shrinkage after 2000°C annealing. They also show an ultrahigh compressive strength of ≈690MPa up to 2000°C, displaying a ductile compressive behavior. The excellent mechanical and thermal insulating properties offer an attractive material for reliable thermal insulation under extreme conditions.

Development of advanced PCR-based methods for accurate identification and authentication of commercial shrimp products

Shrimp is among the most economically valuable and susceptible seafood species to food fraud worldwide. The identities of 40 commercial shrimp products sold in South Korean markets were assessed using the standard barcoding method, revealing a significant 70% incidence of mislabeling. Based on these findings, three distinct PCR methods were developed to differentiate between eight predominant species (Penaeus vannamei, Pandalus borealis, Palaemon gravieri, Leptochela gracilis, Penaeus monodon, Pleoticus muelleri, Metapenaeopsis dalei, and Euphausia pacifica). Both conventional and real-time PCR (RT-PCR) showed specificity ranging from 0.0001 to 0.001 ng/μL, with no cross-reactivity against 18 reference species. These methods were further refined to create a multiplex ultrafast RT-PCR technique that could simultaneously identify seven shrimp species within 23 min while maintaining analytical accuracy that can be adapted for various analytical settings, field applications, rapid screening, quality control, and regulatory compliance, making them invaluable tools for the food industry and regulatory authorities.

Solvent-dependent ultrafast deactivation processes with phenylpropyl indigo derivatives: a step forward in the understanding of indigo decay mechanisms.

Two indigo derivatives, N-phenylpropylindigo (NPhC3Ind) and N,N'-diphenylpropylindigo (N,N'PhC3Ind), were synthesized using green chemistry techniques and their decay mechanisms were elucidated from ultrafast spectroscopic techniques, as well as density functional theory (DFT) and time-dependent DFT (TDDFT) studies. For NPhC3Ind, in methylcyclohexane (MCH) and n-dodecane, a very fast (<1 ps) excited state proton transfer (ESPT) process is observed. In contrast, a bi-exponential decay is found in 2-methyltetrahydrofuran (2MeTHF), with a rising component of 9 ps and a decay of 72 ps, reminiscent of the behavior observed in indigo (IND). DFT/TDDFT calculations rationalize that the excitation of an intermolecular dimer structure, formed between hydrogen bonds involving the CO and H-N of two NPhC3Ind units, leads to the formation of dark (S1) and bright (S2) states. Due to the structural distortion of the dimer, the emission is localized in one of the monomer units. Consequently, the absorption is considered to originate from a dimer while the emission (locally excited state, LE) originates from a monomer unit. In the case of N,N'PhC3Ind, the formation of two conformers (CIN and COUT) in the excited state is observed in viscous solvents, collapsing into a single conformer in 2MeTHF.

Nanoscale and ultrafast in situ techniques to probe plasmon photocatalysis

Plasmonic photocatalysis uses the light-induced resonant oscillation of free electrons in a metal nanoparticle to concentrate optical energy for driving chemical reactions. By altering the joint electronic structure of the catalyst and reactants, plasmonic catalysis enables reaction pathways with improved selectivity, activity, and catalyst stability. However, designing an optimal catalyst still requires a fundamental understanding of the underlying plasmonic mechanisms at the spatial scales of single particles, at the temporal scales of electron transfer, and in conditions analogous to those under which real reactions will operate. Thus, in this review, we provide an overview of several of the available and developing nanoscale and ultrafast experimental approaches, emphasizing those that can be performed in situ. Specifically, we discuss high spatial resolution optical, tip-based, and electron microscopy techniques; high temporal resolution optical and x-ray techniques; and emerging ultrafast optical, x-ray, tip-based, and electron microscopy techniques that simultaneously achieve high spatial and temporal resolution. Ab initio and classical continuum theoretical models play an essential role in guiding and interpreting experimental exploration, and thus, these are also reviewed and several notable theoretical insights are discussed.