Time-resolved X-ray Research Articles

Luminescent color modulation of Zn/BaAl2O4:0.2%Eu phosphors for LED application

Spinel-type aluminate (ZnAl2O4) doped with europium (Eu) ions has garnered considerable attention in the field of luminescence. This study explores a series of Zn/BaAl2O4:0.2%Eu phosphors (x=0∼0.25, x is for the mole fraction of BaAl2O4), fabricated through a high temperature solid-phase reaction method in air or reduction environment. In the case of phosphors synthesized in air, the photoluminescence emission (PL) spectra show a series of sharp emission peaks at 570nm, 589nm, 620nm, 660nm, and 710nm, which are generated by the 5D0-7FJ (J = 0, 1, 2, 3, 4) level transitions in Eu3+. Time-resolved photoluminescence and X-ray photoelectron spectroscopy (XPS) characteristics also validate the presence of Eu3+ in samples synthesized in air. An intriguing observation is the abnormally strong emission peak at 570nm under 346nm excitation, originating from the Eu3+5D0-7F0 level transition. For x=0.15, the corresponding CIE color coordinate is (0.3246, 0.3449), suggesting its potential application as a mono-doped and uni-matrix white phosphor. On the other hand, phosphors synthesized in reduction environment exhibit PL spectra with a wide emission band spanning from 400nm to 550nm, resulting from the electric-dipole-allowed transition of f-d state of Eu2+. The partial substitution of Zn2+ with Ba2+ significantly enhances the Eu2+ luminescence intensity. Moreover, an elevation of the mole fraction of Zn/BaAl2O4:0.2%Eu leads to a notable redshift (450nm→500nm) in the emission peaks of Eu2+ caused by lattice expansion, providing the adjustability of emitting color.

Time-resolved x-ray imaging of nanoscale spin-wave dynamics at multi-GHz frequencies using low-alpha synchrotron operation

Time-resolved x-ray microscopy is used in a low-alpha synchrotron operation mode to image spin dynamics at an unprecedented combination of temporal and spatial resolution. Thereby, nanoscale spin waves with wavelengths down to 70 nm and frequencies up to 30 GHz are directly observed in ferromagnetic thin film microelements with spin vortex ground states. In an antiparallel ferromagnetic bilayer system, we detect the propagation of both optic and acoustic modes, the latter exhibiting even a strong non-reciprocity. In single-layer systems, quasi-uniform spin waves are observed together with modes of higher order (up to the 4th order), bearing precessional nodes over the thickness of the film. Furthermore, the effects of magnetic material properties, film thickness, and magnetic fields on the spin-wave spectrum are determined experimentally. Our experimental results are consistent with numerical calculations from a micromagnetic theory even on these so-far unexplored time- and length scales.

Tracking Minority Species in Redox Reactions: A Quantitative Combined XAS and Modulation Excitation Study.

Understanding the nature of intermediates/active species in reactions is a major challenge in chemistry. This is because spectator species typically dominate the experimentally derived data and consequently active phase contributions are masked. Transient methods offer a means to bypass this difficulty. In particular, modulation excitation with phase-sensitive detection (ME-PSD) provides a mechanism to distinguish between spectator and reacting species. Herein, modulation excitation (ME) time-resolved (energy dispersive) X-ray absorption spectroscopy, assisted by phase sensitive detection (PSD) analysis, has been applied to the study of a liquid phase process; in this case the classic ferrocyanide/ferricyanide redox couple. Periodic switches of the electrical potential (anodic/cathodic) enabled the use of the ME approach. Structural changes at fractions as low as 2 % of the total number of electroactive species were detected within the X-ray beam probe volume containing ~30 pmol of Fe(II)/Fe(III).

Oscillating Structural Transformations in the Electrochemical Synthesis of Graphene Oxide from Graphite.

Electrochemical synthesis of graphene oxide (GO) is known to occur with potential oscillations, but the structural changes underlying these oscillations have remained unclear. In situ time-resolved synchrotron radiation X-ray diffraction demonstrates that the electrochemical synthesis of GO in aqueous H2SO4 can be described as an oscillating reaction. The transformation from graphite to GO proceeds through periodic structural oscillations that correlate with potential cycles. Stage-1 graphite intercalation compound (GIC) is found only at the peak of the potential cycle, but not at the bottom of the cycle. Stage-1 GIC is formed in the first half-cycle from stage-2 GIC and then transforms into "pristine graphite oxide" (PGO) on the lower side of the potential cycle, after which the cycle restarts with the formation of a new portion of stage-1 GIC. Water-washing results in the transformation of PGO into water-swollen GO with d(001) ~11 Å. These periodic structural changes can be considered a new type of oscillating reaction. The presented results provide broad insights into the oscillating structural changes occurring during the anodic graphite oxidation in aqueous H2SO4 and allow to update of the mechanism of GO electrochemical formation.

Flash Flow-Induced Crystallization of Poly(l-lactide) under Elevated Pressure during Industrial-Scale Injection Molding Revealed by Time-Resolved Synchrotron X-ray Scattering

Flash Flow-Induced Crystallization of Poly(<scp>l</scp>-lactide) under Elevated Pressure during Industrial-Scale Injection Molding Revealed by Time-Resolved Synchrotron X-ray Scattering

Dephosphorylation and ion binding in prokaryotic calcium transport

Calcium (Ca 2+ ) signaling is fundamental to cellular processes in both eukaryotic and prokaryotic organisms. While the mechanisms underlying eukaryotic Ca 2+ transport are well documented, an understanding of prokaryotic transport remains nascent. LMCA1, a Ca 2+ adenosine triphosphatase (ATPase) from Listeria monocytogenes , has emerged as a prototype for elucidating structure and dynamics in prokaryotic Ca 2+ transport. Here, we used a multidisciplinary approach integrating kinetics, structure, and dynamics to unravel the intricacies of LMCA1 function. A cryo–electron microscopy (cryo-EM) structure of a Ca 2+ -bound E1 state showed ion coordination by Asp 720 , Asn 716 , and Glu 292 . Time-resolved x-ray solution scattering experiments identified phosphorylation as the rate-determining step. A cryo-EM E2P state structure exhibited remarkable similarities to a SERCA1a E2-P* state, which highlights the essential role of the unique P-A domain interface in enhancing dephosphorylation rates and reconciles earlier proposed mechanisms. Our study underscores the distinctiveness between eukaryotic and prokaryotic Ca 2+ ATPase transport systems and positions LMCA1 as a promising drug target for developing antimicrobial strategies.

Nanosecond-Lived Excimer Observation in a Crystal of a Rhodium(I) Complex via Time-Resolved X-ray Laue Diffraction.

The rare observation of transient Rh···Rh excimer formation in a single crystal is reported. The estimated excited-state lifetime at 100 K is 2 ns, which makes it the shortest-lived small-molecule species caught experimentally using the laser-pump/X-ray-probe time-resolved Laue method. Upon excitation with 390 nm laser light, the intermolecular Rh···Rh distance decreases from 3.379(4) to 3.19(1) Å, and the metal-metal contact gains more bonding character. On the basis of the experimental results and theoretical modeling, the structural changes determined with 100 ps time resolution reflect principally the S0 → S1 electronic transition.

From Ions to Crystals: A Comprehensive View of the Non-Classical Nucleation of Calcium Sulfate.

After years ofintensive research andnumerous important observations, our understanding of the early stages of crystallization is still limited due to the complexity of the underlying processes and their elusive character. In the present work, we provide a detailed view on the nucleation of calcium sulfate mineralization - an abundant mineral with broad use in construction industry - in aqueous systems at ambient conditions. As experimental basis, a co-titration procedure with potentiometric, turbidimetric and conductometric detection was developed, allowing solution speciation and the formation of crystallization precursors to be monitored quantitatively as the level of nominal (super)saturation gradually increases. The nature and spatiotemporal evolution of these precursors was further elucidated by time-resolved small-angle X-ray scattering (SAXS) and analytical ultracentrifugation (AUC) experiments, complemented by cryogenic transmission electron microscopy (cryo-TEM) as a direct imaging technique. The results reveal how ions associate into nanometric primary species, which subsequently aggregate and develop anisotropic order by intrinsic structural reorganization. Our observations challenge the common understanding of fundamental notions such as the nucleation barrier or the meaning of supersaturation, with broad implications for mineralization phenomena in general and the formation of calcium sulfate in geochemical settings and industrial applications in particular.

Ultrafast Yttrium Hydride Chemistry at High Pressures via Non-equilibrium States Induced by an X-ray Free Electron Laser.

Controlling the formation and stoichiometric content of the desired phases of materials has become of central interest for a variety of fields. The possibility of accessing metastable states by initiating reactions by X-ray-triggered mechanisms over ultrashort time scales has been enabled by the development of X-ray free electron lasers (XFELs). Utilizing the exceptionally high-brilliance X-ray pulses from the EuXFEL, we report the synthesis of a previously unobserved yttrium hydride under high pressure, along with nonstoichiometric changes in hydrogen content as probed at a repetition rate of 4.5 MHz using time-resolved X-ray diffraction. Exploiting non-equilibrium pathways, we synthesize and characterize a hydride in a Weaire-Phelan structure type at pressures as low as 125 GPa, predicted using a crystal structure search, with a hydrogen content of 4.0-5.75 hydrogens per cation, that is enthalpically metastable on the convex hull.

Glass-like Relaxation Dynamics during the Disorder-to-Order Transition of Viral Nucleocapsids.

Nucleocapsid self-assembly is an essential yet elusive step in virus replication. Using time-resolved small-angle X-ray scattering on a model icosahedral ssRNA virus, we reveal a previously unreported kinetic pathway. Initially, RNA-bound capsid subunits rapidly accumulate beyond the stoichiometry of native virions. This is followed by a disorder-to-order transition characterized by glass-like relaxation dynamics and the release of excess subunits. Our molecular dynamics simulations, employing a coarse-grained elastic model, confirm the physical feasibility of self-ordering accompanied by subunit release. The relaxation can be modeled by an exponential integral decay on the mean squared radius of gyration, with relaxation times varying within the second range depending on RNA type and subunit concentration. A nanogel model suggests that the initially disordered nucleoprotein complexes quickly reach an equilibrium size, while their mass fractal dimension continues to evolve. Understanding virus self-assembly is not only crucial for combating viral infections, but also for designing synthetic virus-inspired nanocages for drug delivery applications.

Revealing the Role of Ruthenium on the Performance of P2-Type Na0.67Mn1-xRuxO2 Cathodes for Na-Ion Full-Cells.

Herein, P2-type layered manganese and ruthenium oxide is synthesized as an outstanding intercalation cathode material for high-energy density Na-ion batteries (NIBs). P2-type sodium deficient transition metal oxide structure, Na0.67Mn1-xRuxO2 cathodes where x varied between 0.05 and 0.5 are fabricated. The partially substituted main phase where x = 0.4 exhibits the best electrochemical performance with a discharge capacity of ≈170mAhg-1. The in situ X-ray Absorption Spectroscopy (XAS) and time-resolved X-ray Diffraction (TR-XRD) measurements are performed to elucidate the neighborhood of the local structure and lattice parameters during cycling. X-ray photoelectron spectroscopy (XPS) revealed the oxygen-rich structure when Ru is introduced. Density of States (DOS) calculations revealed the Fermi-Level bandgap increases when Ru is doped, which enhances the electronic conductivity of the cathode. Furthermore, magnetization calculations revealed the presence of stronger Ru─O bonds and the stabilizing effect of Ru-doping on MnO6 octahedra. The results of Time-of-flight secondary-ion mass spectroscopy (TOF-SIMS) revealed that the Ru-doped sample has more sodium and oxygenated-based species on the surface, while the inner layers mainly contain Ru-O and Mn-O species. The full cell study demonstrated the outstanding capacity retention where the cell maintained 70% of its initial capacity at 1C-rate after 500 cycles.

Identifying, quantifying, and mitigating background with the time-resolved x-ray diffraction platform at the National Ignition Facility.

The time-resolved x-ray diffraction platform at the National Ignition Facility (NIF) fields electronic sensors closer to the exploding laser-driven target than any other NIF diagnostic in order to directly detect diffracted x rays from highly compressed materials. We document strategies to characterize and mitigate the unacceptably high background signals observed in this geometry. We specifically assess the possible effects of electromagnetic pulse, x-ray fluorescence, hot electrons, and sensor-specific non-x-ray artifacts. Significant background reduction is achieved by strategic shielding.

Steerable current-driven emission of spin waves in magnetic vortex pairs.

The efficient excitation of spin waves is a key challenge in the realization of magnonic devices. We demonstrate current-driven generation of spin waves in antiferromagnetically coupled magnetic vortices. We use time-resolved x-ray microscopy to directly image the emission of spin waves upon the application of alternating currents flowing directly through the magnetic stack. Micromagnetic simulations allow us to identify the current-driven Oersted field as the main origin of excitation, in contrast to spin-transfer torques. In our case, these internal Oersted fields have an orders of magnitude higher spin-wave excitation efficiency than commonly used stripline antennas. For magnetostrictive materials, we furthermore demonstrate that the direction of magnon propagation can be steered by increasing the excitation amplitude, which modifies the underlying magnetization profile through an additional anisotropy. The demonstrated methods allow for the efficient and tunable excitation of spin waves, marking a substantial advance concerning the design of magnonic devices.

Time-resolved Auger-Meitner spectroscopy of the photodissociation dynamics of CS2

Abstract The photodissociation dynamics of UV excited CS2 are investigated using time-resolved Auger-Meitner spectroscopy. Auger-Meitner decay is initiated by inner-shell ionisation with a femtosecond duration X-ray (179.9 eV) probe generated by the FERMI free electron laser. The time-delayed X-ray probe removes an electron from the S(2p) orbital leading to secondary emission of a high energy electron through Auger-Meitner decay. We monitor the electron kinetic energy of the Auger-Meitner emission as a function of pump-probe delay and observe time-dependent changes in the spectrum that correlate with the formation of bound, excited-state CS2 molecules at early times, and CS + S fragments on the picosecond timescale. The results are analysed based on a simplified kinetic scheme that provides a time constant for dissociation of approximately 1.2 ps, in agreement with previous time-resolved X-ray photoelectron spectroscopy measurements (Gabalski, et al. J. Phys. Chem. Lett. 2023, 14, 7126–7133).

Metastable water at several compression rates and its freezing kinetics into ice VII

Water can be dynamically over-compressed well into the stability field of ice VII. Whether water then transforms into ice VII, vitreous ice or a metastable novel crystalline phase remained uncertain. We report here the freezing of over-compressed water to ice VII by time-resolved X-ray diffraction. Quasi-isothermal dynamic compression paths are achieved using a dynamic-piezo-Diamond-Anvil-Cell, with programmable pressure rise time from 0.1 ms to 100 ms. By combining the present data set with those obtained on various ns-dynamical platforms, a complete evolution of the solidification pressure of metastable water versus the compression rate is rationalized within the classical nucleation theory framework. Also, when crystallization into ice VII occurs in between 1.6 GPa and 2.0 GPa, that is in the stability field of ice VI, a structural evolution over few ms is then observed into a mixture of ice VI and ice VII that seems to resolve apparent contradictions between previous results.

Combustion synthesis of the (Ti,Zr)B2-(Zr,Ti)C eutectic composites: Structure formation and properties

The macrokinetic characteristics of combustion of the quaternary Ti-Zr-B-C mixture as well as the mechanism and stages of phase formation for the synthesis products were investigated. The mechanical and thermophysical properties of the hot-pressed boride/carbide ceramics with eutectic composition (Ti,Zr)B2-43%at.(Zr,Ti)C were measured. Preliminary mechanical alloying (MA) of the (Zr + Ti) mixture was shown to yield Ti/Zr granules having a laminar structure and consisting of alternating layers of titanium, zirconium, and (Zr,Ti)ss solid solution. The method used to prepare reaction mixtures and the initial temperature T0 increased within the range of 20–370 °C have virtually no effect on combustion temperature, which is 2260–2400 °C, while higher T0 increases the combustion rate by a factor of 1.5–2. The use of MA Ti/Zr granules reduces the combustion rate as well as the specific heat release amount and the heat release rate. Time-resolved X-ray diffraction data showed that binary carbides (Zr1-xTix)C and diborides (Ti1-yZry)B2 of variable stoichiometry are formed in the combustion wave of the Ti-Zr-B-C reaction mixtures within less than 0.25 s. The carbide and diboride phases are formed simultaneously; the use of MA Ti/Zr granules in the reaction mixtures reduces the content of solid solutions of variable stoichiometry among the reaction products. The ceramics fabricated using a combination of combustion synthesis and hot pressing have a dense and homogeneous structure that consist of bonded grains of the diboride (Ti0.80Zr0.20)B2 and carbide (Zr0.83Ti0.17)C phases having the following properties: density, 5.3 g/cm3; hardness, 22.9 GPa; fracture toughness, 4.7 MPa m0.5; heat capacity, 0.52 J/(g·K); thermal diffusivity, 11.67 mm2/s; and thermal conductivity, 33.28 W/(m·K).

Early Events in G-quadruplex Folding Captured by Time-Resolved Small-Angle X-Ray Scattering.

Time-resolved small-angle X-ray experiments (TR-SAXS) are reported here that capture and quantify a previously unknown rapid collapse of the unfolded oligonucleotide as an early step in G4 folding of hybrid 1 and hybrid 2 telomeric G-quadruplex structures. The rapid collapse, initiated by a pH jump, is characterized by an exponential decrease in the radius of gyration from 20.6 to 12.6 Å. The collapse is monophasic and is complete in less than 600 ms. Additional hand-mixing pH-jump kinetic studies show that slower kinetic steps follow the collapse. The folded and unfolded states at equilibrium were further characterized by SAXS studies and other biophysical tools, to show that G4 unfolding was complete at alkaline pH, but not in LiCl solution as is often claimed. The SAXS Ensemble Optimization Method (EOM) analysis reveals models of the unfolded state as a dynamic ensemble of flexible oligonucleotide chains with a variety of transient hairpin structures. These results suggest a G4 folding pathway in which a rapid collapse, analogous to molten globule formation seen in proteins, is followed by a confined conformational search within the collapsed particle to form the native contacts ultimately found in the stable folded form.

Discriminating Clockwise and Counterclockwise Photoisomerization Paths in Achiral Photoswitches by Excited-State Electronic Circular Dichroism.

Despite the numerous investigations of photoisomerization reactions from both the computational and experimental points of view, even in complex environments, to date there is no direct demonstration of the direction of rotation of the retinal chromophore, initiating the vision process in several organisms, occurring upon light irradiation. In the literature, many proposals have been formulated to shed light on the details of this process, most of which are extracted from semiclassical simulations. Although high hopes are held in the development of time-resolved X-ray spectroscopy, I argue in this work that simpler but less known techniques can be used to unravel the details of this fascinating photochemical process. In fact, chiroptical spectroscopy would unambiguously prove the direction of the rotatory motion of the chromophore during the photoisomerization process by probing excited state chirality, a piece of information that, so far, has been exclusively extracted from atomistic simulations. I demonstrate this statement by computing the expected chiroptical response along photoisomerization pathways for several models of the retinal chromophores that are found in nature bound to rhodopsins, including nuclear ensemble spectra from semiclassical dynamics simulations, that can be compared with time-resolved experiments.

Evaluation of molecular interaction between intercellular lipid organization in human stratum corneum and terpenes using time-resolved synchrotron X-ray diffraction

The stratum corneum (SC) presents certain limitations for topical administration of medication, which can be overcome using penetration enhancers (PEs) such as terpene (TP). The SC is also crucial for maintaining the skin barrier and consists of two lamellar structures: the short periodicity phase (SPP) and long periodicity phase (LPP). In this study, we monitored changes in the X-ray diffraction peaks of the human SC, 30 min after TP application (neroridol, 1,8-cineol, and d-limonene). With the application of nerolidol, no significant changes were observed in the small-angle diffraction peak positions for the lamellar structure of SPP, but the integrated intensity decreased. On the contrary, when applying 1,8-cineole and d-limonene, a lower angle peak shift with broadening of the peak width of SPP diffraction peaks was observed for d-limonene than for 1,8-cineole, and the degree of peak shift and width broadening was greater for d-limonene than for 1,8-cineole. The diffraction peaks of LPP disappeared when 1,8-cineole and d-limonene were applied. These results indicate that the degree of interaction between the SC and TP differs depending on the molecular species, and d-limonene and 1,8-cineole exhibit penetration-enhancing via lamellar structure disruption of both SPP and LPP, immediately after application.

A study of an X-ray flare on the solar analogue V895 Tau

Using observations with XMM-Newton, we study the characteristics of a flare emanating from a solar analogous V895 Tau. At the peak of the flare, its luminosity reached 3.3×1030ergs−1, which is ∼ 600 times more energetic than the X10 class flare on the Sun. The quiescent state corona of V895 Tau is depicted by a two-temperature plasma model with temperatures of 3.9 and 11 MK. The flare’s evolution was carefully scrutinized through time-resolved X-ray spectroscopy, unveiling the variations in temperature, emission measure, abundance and luminosity during the flare. The temperature peaked at 36.1 MK, which is approximately four times higher than the pre-flare temperature. Employing a hydrodynamic loop model, we have estimated the half length of the flaring loop to be 5.9×1010 cm. Using the loop scaling laws, other loop parameters like density, pressure, volume, and minimum magnetic field are also estimated, and are found to be similar to those of other flares from similar type of stars.