arXiv subjects

Mariia Filianina

Publications and source records attributed to Mariia Filianina.

14 recordsLinked to original sources

arXiv2026

Liquid-liquid phase separation precedes crystallization in supercooled water-glycerol solutions

Understanding the structural evolution of supercooled water-glycerol solutions is important for cryopreservation, yet distinguishing liquid-state transformations from ice crystallization remains challenging. Here, we investigate a deeply supercooled water-glycerol solution by X-ray photon correlation spectroscopy (XPCS) in ultra-small-angle X-ray scattering (USAXS) geometry, combined with wide-angle X-ray scattering (WAXS). This combination simultaneously captures the structural and dynamical evolution of the supercooled liquid upon quenching to cryogenic temperatures (172 K). We observe discontinuous changes in the liquid structure on molecular length scales and formation of microscale domains. The dynamics slow down during this stage and exhibit hyper-diffusive, ballistic-like relaxation. This transformation precedes ice crystallization, which we identify from the emergence of ice Bragg peaks in WAXS, allowing the two processes to be temporally separated. Phase-field (Cahn-Hilliard) simulations qualitatively reproduce the experimental observations and show that a spinodal-decomposition scenario is consistent with the measured scattering evolution. These findings are consistent with a liquid-liquid phase separation scenario preceding ice crystallization and provide a route to disentangle the two processes in supercooled aqueous systems.

cond-mat.soft↗

arXiv2025

Coherent X-rays reveal anomalous molecular diffusion and cage effects in crowded protein solutions

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 in between the short- and long-time protein diffusion regimes. Modeling with the $δγ$-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 new 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.

cond-mat.soft↗

arXiv2025

Nanoscale Protein Diffusion in Supercooled Cryoprotectant Solutions

Vitrification during cryopreservation requires a quantitative understanding of protein transport in deeply supercooled cryoprotectant solutions, yet direct measurements at molecular length scales remain scarce. Here, we combine X-ray Photon Correlation Spectroscopy (XPCS) and small-angle X-ray scattering (SAXS) to investigate ferritin diffusion in glycerol-water mixtures from ambient conditions down to 210 K. The measured diffusion coefficients reveal that ferritin retains a higher mobility upon cooling than expected from hydrodynamic scaling based on measurements of larger silica reference tracers, with the difference emerging below approximately 230 K. A minimal fluctuating-friction model reproduces the observed relative enhancement in diffusion, illustrating how local variations in the effective friction can give rise to such behavior. These measurements provide direct experimental benchmarks for future theoretical and simulation studies aimed at understanding molecular transport in deeply supercooled liquids approaching the glass transition.

cond-mat.soft↗

arXiv2024

Supercritical density fluctuations and structural heterogeneity in supercooled water-glycerol microdroplets

Recent experiments and theoretical studies strongly indicate that water exhibits a liquid-liquid phase transition (LLPT) in the supercooled domain. An open question is how the LLPT of water can affect the properties of aqueous solutions. Here, we study the structural and thermodynamic properties of supercooled glycerol-water microdroplets at dilute conditions ($χ_g=3.2~\%$ glycerol mole fraction). The combination of rapid evaporative cooling with ultrafast X-ray scattering allows us to outrun crystallization and gain access to the deeply supercooled regime down to $T=229.3$ K. We find that the density fluctuations of the glycerol-water solution or, equivalently, its isothermal compressibility, $κ_T$, increases upon cooling. This is confirmed by molecular dynamics simulations, which indicate that the presence of glycerol shifts the temperature of maximum $κ_T$ from $T=230$ K in pure water down to $T=223$ K in the solution. Our findings elucidate the interplay between the complex behavior of water, including its LLPT, and the properties of aqueous solutions at low temperatures, which can have practical consequences in cryogenic biological applications and cryopreservation techniques.

cond-mat.soft↗

arXiv2023

Nanocrystallites Modulate Intermolecular Interactions in Cryoprotected Protein Solutions

Studying protein interactions at low temperatures has important implications for optimizing cryostorage processes of biological tissue, food, and protein-based drugs. One of the major challenges is related to the formation of ice nanocrystals which can occur even in the presence of cryoprotectants and can lead to protein denaturation. Here, using a combination of small- and wide-angle X-ray scattering (SAXS and WAXS), we investigate the structural evolution of concentrated Lysozyme solutions in a cryoprotected glycerol-water mixture upon cooling from room temperature (T=300 K) down to cryogenic temperatures (T=195 K). Upon cooling, we observe a transition near the melting temperature of the solution (T~245 K), which manifests both in the temperature dependence of the scattering intensity peak position reflecting protein-protein length scales (SAXS) and the interatomic distances within the solvent (WAXS). Upon thermal cycling, a hysteresis is observed in the scattering intensity, which is attributed to the formation of nanocrystallites in the order of 10 nm. The experimental data is well described by the two-Yukawa model, which indicates temperature-dependent changes in the short-range attraction of the protein-protein interaction potential. Our results demonstrate that the nanocrystal growth yields effectively stronger protein-protein attraction and influences the protein pair distribution function beyond the first coordination shell.

cond-mat.soft↗

arXiv2023

Coherent X-ray Scattering Reveals Nanoscale Fluctuations in Hydrated Proteins

Hydrated proteins undergo a transition in the deeply supercooled regime, which is attributed to rapid changes in hydration water and protein structural dynamics. Here, we investigate the nanoscale stress relaxation in hydrated lysozyme proteins stimulated and probed by X-ray Photon Correlation Spectroscopy (XPCS). This approach allows us to access the nanoscale dynamic response in the deeply supercooled regime (T = 180 K) which is typically not accessible through equilibrium methods. The relaxation time constants exhibit Arrhenius temperature dependence upon cooling with a minimum in the Kohlrausch-Williams-Watts exponent at T = 227 K. The observed minimum is attributed to an increase in dynamical heterogeneity, which coincides with enhanced fluctuations observed in the two-time correlation functions and a maximum in the dynamic susceptibility quantified by the normalised variance $χ_T$. Our study provides new insights into X-ray stimulated stress relaxation and the underlying mechanisms behind spatio-temporal fluctuations in biological granular materials.

cond-mat.soft↗

arXiv2022

Resolving molecular diffusion and aggregation of antibody proteins with megahertz X-ray free-electron laser pulses

X-ray free-electron lasers (XFELs) with megahertz repetition rate can provide novel insights into structural dynamics of biological macromolecule solutions. However, very high dose rates can lead to beam-induced dynamics and structural changes due to radiation damage. Here, we probe the dynamics of dense antibody protein (Ig-PEG) solutions using megahertz X-ray photon correlation spectroscopy (MHz-XPCS) at the European XFEL. By varying the total dose and dose rate, we identify a regime for measuring the motion of proteins in their first coordination shell, quantify XFEL-induced effects such as driven motion, and map out the extent of agglomeration dynamics. The results indicate that for average dose rates below $1.06\,\mathrm{kGy}\mathrm{μs}^{-1}$ in a time window up to $10\,\mathrm{μs}$, it is possible to capture the protein dynamics before the onset of beam induced aggregation. We refer to this approach as correlation before aggregation and demonstrate that MHz-XPCS bridges an important spatio-temporal gap in measurement techniques for biological samples.

physics.bio-ph↗

arXiv2022

Identifiying the domain wall spin structure in current-induced switching of antiferromagnetic NiO/Pt

The understanding of antiferromagnetic domain walls, which are the interface between domains with different Néel order orientations, is a crucial aspect to enable the use of antiferromagnetic materials as active elements in future spintronic devices. In this work, we demonstrate that in antiferromagnetic NiO/Pt bilayers circular domain structures can be generated by switching driven by electrical current pulses. The generated domains are T-domains, separated from each other by a domain wall whose spins are pointing toward the average direction of the two T-domains rather than the common axis of the two planes. Interestingly, this direction is the same for the whole circular domain indicating the absence of strong Lifshitz invariants. The domain wall can be micromagnetically modeled by strain distributions in the NiO thin film induced by the MgO substrate, deviating from the bulk anisotropy. From our measurements we determine the domain wall width to have a full width at half maximum of $Δ= 98 \pm 10$ nm, demonstrating strong confinement.

cond-mat.mtrl-sci↗

arXiv2022

Optically-triggered strain-driven Néel vector manipulation in a metallic antiferromagnet

The absence of stray fields, their insensitivity to external magnetic fields, and ultrafast dynamics make antiferromagnets promising candidates for active elements in spintronic devices. Here, we demonstrate manipulation of the Néel vector in the metallic collinear antiferromagnet Mn$_2$Au by combining strain and femtosecond laser excitation. Applying tensile strain along either of the two in-plane easy axes and locally exciting the sample by a train of femtosecond pulses, we align the Néel vector along the direction controlled by the applied strain. The dependence on the laser fluence and strain suggests the alignment is a result of optically-triggered depinning of 90$^{\mathrm{o}}$ domain walls and their sliding in the direction of the free energy gradient, governed by the magneto-elastic coupling. The resulting, switchable, state is stable at room temperature and insensitive to magnetic fields. Such an approach may provide ways to realize robust high-density memory device with switching timescales in the picosecond range.

cond-mat.mtrl-sci↗

arXiv2021

Optical read-out of the Néel vector in metallic antiferromagnet Mn$_{2}$Au

Metallic antiferromagnets with broken inversion symmetry on the two sublattices, strong spin-orbit coupling and high Néel temperatures offer new opportunities for applications in spintronics. Especially Mn$_{2}$Au, with high Néel temperature and conductivity, is particularly interesting for real-world applications. Here, manipulation of the orientation of the staggered magnetization,\textit{\ i.e.} the Néel vector, by current pulses has been recently demonstrated, with the read-out limited to studies of anisotropic magnetoresistance or X-ray magnetic linear dichroism. Here, we report on the in-plane reflectivity anisotropy of Mn$_{2}$Au (001) films, which were Néel vector aligned in pulsed magnetic fields. In the near-infrared, the anisotropy is $\approx$ 0.6\%, with higher reflectivity for the light polarized along the Néel vector. The observed magnetic linear dichroism is about four times larger than the anisotropic magnetoresistance. This suggests the dichroism in Mn$_{2}$Au is a result of the strong spin-orbit interactions giving rise to anisotropy of interband optical transitions, in-line with recent studies of electronic band-structure. The considerable magnetic linear dichroism in the near-infrared could be used for ultrafast optical read-out of the Néel vector in Mn$_{2}$Au.

cond-mat.mtrl-sci↗

arXiv2021

Full angular dependence of the spin Hall and ordinary magnetoresistance in epitaxial antiferromagnetic NiO(001)/Pt thin films

We report the observation of the three-dimensional angular dependence of the spin Hall magnetoresistance (SMR) in a bilayer of the epitaxial antiferromagnetic insulator NiO(001) and the heavy metal Pt, without any ferromagnetic element. The detected angular-dependent longitudinal and transverse magnetoresistances are measured by rotating the sample in magnetic fields up to 11 T, along three orthogonal planes (xy-, yz- and xz-rotation planes, where the z-axis is orthogonal to the sample plane). The total magnetoresistance has contributions arising from both the SMR and ordinary magnetoresistance. The onset of the SMR signal occurs between 1 and 3 T and no saturation is visible up to 11 T. The three-dimensional angular dependence of the SMR can be explained by a model considering the reversible field-induced redistribution of magnetostrictive antiferromagnetic S- and T-domains in the NiO(001), stemming from the competition between the Zeeman energy and the elastic clamping effect of the non-magnetic MgO substrate. From the observed SMR ratio, we estimate the spin mixing conductance at the NiO/Pt interface to be greater than $2\times10^{14}$ $Ω^{-1}$ $m^{-2}$. Our results demonstrate the possibility to electrically detect the Néel vector direction in stable NiO(001) thin films, for rotations in the xy- and xz- planes. Moreover, we show that a careful subtraction of the ordinary magnetoresistance contribution is crucial to correctly estimate the amplitude of the SMR.

cond-mat.mtrl-sci↗

arXiv2021

Identification of Néel vector orientation in antiferromagnetic domains switched by currents in NiO/Pt thin films

Understanding the electrical manipulation of antiferromagnetic order is a crucial aspect to enable the design of antiferromagnetic devices working at THz frequency. Focusing on collinear insulating antiferromagnetic NiO/Pt thin films as a materials platform, we identify the crystallographic orientation of the domains that can be switched by currents and quantify the Néel vector direction changes. We demonstrate electrical switching between different T-domains by current pulses, finding that the Néel vector orientation in these domains is along $[\pm5\ \pm5\ 19]$, different compared to the bulk $<11\bar{2}>$ directions. The final state of the Néel vector $\textbf{n}$ switching after current pulses $\textbf{j}$ along the $[1\ \pm1\ 0]$ directions is $\textbf{n}\parallel \textbf{j}$. By comparing the observed Néel vector orientation and the strain in the thin films, assuming that this variation arises solely from magnetoelastic effects, we quantify the order of magnitude of the magnetoelastic coupling coefficient as $b_{0}+2b_{1}=3*10^7 J\ m^{-3}$ . This information is key for the understanding of current-induced switching in antiferromagnets and for the design and use of such devices as active elements in spintronic devices.

cond-mat.mtrl-sci↗

arXiv2020

Electric-field control of spin-orbit torques in perpendicularly magnetized W/CoFeB/MgO films

Controlling magnetism by electric fields offers a highly attractive perspective for designing future generations of energy-efficient information technologies. Here, we demonstrate that the magnitude of current-induced spin-orbit torques in thin perpendicularly magnetized CoFeB films can be tuned and even increased by electric field generated piezoelectric strain. Using theoretical calculations, we uncover that the subtle interplay of spin-orbit coupling, crystal symmetry, and orbital polarization is at the core of the observed strain dependence of spin-orbit torques. Our results open a path to integrating two energy efficient spin manipulation approaches, the electric field-induced strain and the current-induced magnetization switching, thereby enabling novel device concepts.

cond-mat.mes-hall↗

arXiv2019

Mechanism of Néel order switching in antiferromagnetic thin films revealed by magnetotransport and direct imaging

We probe the current-induced magnetic switching of insulating antiferromagnet/heavy metals systems, by electrical spin Hall magnetoresistance measurements and direct imaging, identifying a reversal occurring by domain wall (DW) motion. We observe switching of more than one third of the antiferromagnetic domains by the application of current pulses. Our data reveal two different magnetic switching mechanisms leading together to an efficient switching, namely the spin-current induced effective magnetic anisotropy variation and the action of the spin torque on the DWs.

cond-mat.mtrl-sci↗