Alexey Zozulya

Even on the nanoscale, phase transitions are governed by both intrinsic and extrinsic heterogeneities, yet capturing their spatio-temporal dynamics remains a challenge. While ultrafast techniques track phase changes on femtosecond timescales, the spatial complexity and stochastic nature of the processes often remain hidden. Here, we present an experimental approach that combines established ultrafast hard-X-ray diffraction with a propagating strain pulse as a universal and non-invasive structural marker. This ultrafast X-ray sonography identifies the spatio-temporal structural phase heterogeneity on nanometer length- and picosecond time-scales by tracking the phase-specific strain response. It offers a versatile platform for investigating a wide range of phase transitions accompanied by structural changes in typical nanometer-thin films. We apply this approach to the antiferromagnetic-to-ferromagnetic magneto-structural phase transition in FeRh. Modeling the phase-specific strain response identifies the nucleation of domains of approximately 20 nm height exhibiting the structural signatures of the ferromagnetic phase.

Macromolecular crowding plays a crucial role in modulating protein dynamics in cellular and in vitro environments. Polymeric crowders such as dextran and Ficoll are known to induce entropic forces, including depletion interactions, that promote structural organization, yet their nanoscale consequences for protein dynamics remain poorly understood. Here, we employ megahertz X-ray photon correlation spectroscopy (MHz-XPCS) at the European X-ray Free Electron Laser (XFEL) to probe the dynamics of the protein ferritin in solutions containing sucrose, dextran, and Ficoll. We find pronounced changes in collective protein dynamics in polymeric crowders, revealing depletion-driven short-range attractions that, combined with long-range repulsions, give rise to intermediate-range organization. These mesoscale correlations undergo collective relaxation on microsecond to millisecond timescales, as directly resolved by XPCS through the decay of ferritin density fluctuations. The magnitude of this depends sensitively on crowder molecular weight and type. Normalizing the crowder concentration by c * reveals scaling behavior of ferritin self-diffusion with a crossover near 2 c *, marking a transition from depletion-enhanced mobility to viscosity-dominated slowing. Our results demonstrate that bulk properties alone are insufficient to describe protein dynamics in crowded solutions, highlighting the need to include polymer-specific interactions and depletion theory in models of crowded environments.

In this article, we present the experimental protocol and data-processing framework for megahertz X-ray Photon Correlation Spectroscopy (MHz-XPCS) experiments on soft matter samples implemented at the Materials Imaging and Dynamics (MID) instrument of the European X-ray Free-Electron Laser (EuXFEL). Due to the introduction of a standard configuration and the implementation of a highly automated data-processing pipeline, MHz-XPCS measurements can now be conducted and analyzed with minimal user intervention. A key challenge lies in managing the extremely large data volumes generated by the Adaptive Gain Integrating Pixel Detector (AGIPD) – often reaching several petabytes within a single experiment. We describe the technical implementation, discuss the hardware requirements related to effective parallel data processing and propose strategies to enhance data quality, in particular related to data reduction strategies and an improvement of the signal-to-noise ratio. Finally, we address strategies for making the processed data FAIR (Findable, Accessible, Interoperable, Reusable), in alignment with the goals of the DAPHNE4NFDI project.

We report transient highly strained structural states in individual palladium (Pd) nanocrystals, electronically heated using an optical laser, which precede their uniform thermal expansion. Using an X-ray free-electron laser probe, the evolution of individual 111 Bragg peaks is measured as a function of delay time at various laser fluences. Above a laser fluence threshold at a sufficient pump-probe delay, the Bragg peak splits into multiple peaks, indicating heterogeneous strain, before returning to a single peak, corresponding to even heat distribution throughout the lattice expanded crystal. Our findings are supported by a lattice displacement and strain model of a single nanocrystal at different delay times, which agrees with the experimental data. Our observations have implications for understanding femtosecond laser interactions with metals and the potential photo-catalytic performance of Pd.

Understanding protein motion within the cell is crucial for predicting reaction rates and macromolecular transport in the cytoplasm. A key question is how crowded environments affect protein dynamics through hydrodynamic and direct interactions at molecular length scales. Using megahertz X-ray Photon Correlation Spectroscopy (MHz-XPCS) at the European X-ray Free Electron Laser (EuXFEL), we investigate ferritin diffusion at microsecond time scales. Our results reveal anomalous diffusion, indicated by the non-exponential decay of the intensity autocorrelation function g ₂ ( q , t ) at high concentrations. This behavior is consistent with the presence of cage-trapping between the short- and long-time protein diffusion regimes. Modeling with the δ γ -theory of hydrodynamically interacting colloidal spheres successfully reproduces the experimental data by including a scaling factor linked to the protein direct interactions. These findings offer insights into the complex molecular motion in crowded protein solutions, with potential applications for optimizing ferritin-based drug delivery, where protein diffusion is the rate-limiting step.

We demonstrate an advanced scattering method for accessing the 3D reciprocal space of crystalline structures forming in a rapidly supercooled noble-gas liquid using a combination of femtosecond X-ray diffraction and X-ray cross-correlation analysis. The preservation of angular information from the scattering signal allows probing the structure factor along selected directions in reciprocal space and identifying signatures undetectable in azimuthally integrated scattering curves. Therefore, more information from serial diffraction experiments on stochastic crystallization processes can be retrieved despite the inherent variation of the crystal orientation and morphology for each single probe. We also demonstrate how different features in the correlation maps can be associated with certain forms of stacking faults, which enables studying such defects in situ and disentangling them from simultaneous changes in crystal size and temperature.

The structural and dynamical properties of soft-matter systems play an important role in crystallization and nucleation theory. Despite their significance, the dynamical properties are still poorly understood because of experimental constraints and the requirement of performing measurements with high spatial and temporal resolution. Here, we demonstrate MHz X-ray photon correlation spectroscopy (XPCS) using a contactless sample holder at the European X-ray Free-Electron Laser. A millimetre-sized liquid sample droplet was levitated in air via acoustic waves with the solvent slowly evaporating. A colloidal suspension of silica nanospheres was used to track the structural evolutions using small-angle X-ray scattering, and the dynamical information was captured by time-resolved MHz XPCS as a function of evaporation time. This study outlines a new path towards the investigation of metastable structure and dynamics using X-ray speckle techniques, for instance, XPCS, X-ray speckle visibility spectroscopy and X-ray cross-correlation analysis.

In spite of four decades of research on vitrified glassy water droplets, their flow properties in the deeply supercooled regime below 160 K have remained elusive. However, they are key to astrophysical processes where molecules are transported between water interfaces in the deeply supercooled or glassy state. Here we observe coalescence of a deposit consisting of thousands of micrometer-sized glassy water droplets between ~123 and ~140 K. Both electron microscopy and small-angle X-ray scattering indicate the disappearance of droplet interfaces at the time scale of minutes. Scattering profiles suggest a mechanism involving stretching of droplets and confluence. Remarkably, these phenomena coincide with water’s first glass transition, which thus defines the verge between glassy and liquid water. This marks the observation of coalescence in the ultraviscous domain, whereas previously coalescence has only been recognized for temperatures above 260 K, at which viscosity is thirteen orders of magnitude lower. Our findings indicate a recoupling of viscosity to translational diffusion below 160 K, while decoupling and breakdown of the Stokes-Einstein relation take place above 250 K. Coalescence under cryoconditions might take place in grainy amorphous ice covering interstellar dust particles in molecular clouds, enabling the formation of complex molecules in space.

Dark field x-ray microscopy (DXFM) can visualize microstructural distortions in bulk crystals. Using the femtosecond x-ray pulses generated by x-ray free-electron lasers (XFELs), DFXM can achieve sub-μm spatial resolution and <100 fs time resolution simultaneously. In this paper, we demonstrate ultrafast DFXM measurements at the European XFEL to visualize an optically driven longitudinal strain wave propagating through a diamond single crystal. We also present two DFXM scanning modalities that are new to the XFEL sources: spatial 3D and 2D axial-strain scans with sub-μm spatial resolution. With this progress in XFEL-based DFXM, we discuss new opportunities to study multi-timescale spatiotemporal dynamics of microstructures.

The liquid-to-solid phase transition is a complex process that is difficult to investigate experimentally with sufficient spatial and temporal resolution. A key aspect of the transition is the formation of a critical seed of the crystalline phase in a supercooled liquid, that is, a liquid in a metastable state below the melting temperature. This stochastic process is commonly described within the framework of classical nucleation theory, but accurate tests of the theory in atomic and molecular liquids are challenging. Here, we employ femtosecond x-ray diffraction from microscopic liquid jets to study crystal nucleation in supercooled liquids of the rare gases argon and krypton. Our results provide stringent limits to the validity of classical nucleation theory in atomic liquids, and offer the long-sought possibility of testing nonclassical extensions of the theory.