Low-density Domains Research Articles

Unraveling the dynamic slowdown in supercooled water: The role of dynamic disorder in jump motions.

When a liquid is rapidly cooled below its melting point without inducing crystallization, its dynamics slow down significantly without noticeable structural changes. Elucidating the origin of this slowdown has been a long-standing challenge. Here, we report a theoretical investigation into the mechanism of the dynamic slowdown in supercooled water, a ubiquitous yet extraordinary substance characterized by various anomalous properties arising from local density fluctuations. Using molecular dynamics simulations, we found that the jump dynamics, which are elementary structural change processes, deviate from Poisson statistics with decreasing temperature. This deviation is attributed to slow variables competing with the jump motions, i.e., dynamic disorder. The present analysis of the dynamic disorder showed that the primary slow variable is the displacement of the fourth nearest oxygen atom of a jumping molecule, which occurs in an environment created by the fluctuations of molecules outside the first hydration shell. As the temperature decreases, the jump dynamics become slow and intermittent. These intermittent dynamics are attributed to the prolonged trapping of jumping molecules within extended and stable low-density domains. As the temperature continues to decrease, the number of slow variables increases due to the increased cooperative motions. Consequently, the jump dynamics proceed in a higher-dimensional space consisting of multiple slow variables, becoming slower and more intermittent. It is then conceivable that with further decreasing temperature, the slowing and intermittency of the jump dynamics intensify, eventually culminating in a glass transition.

Beyond Local Structures in Critical Supercooled Water through Unsupervised Learning.

The presence of a second critical point in water has been a topic of intense investigation for the last few decades. The molecular origins underlying this phenomenon are typically rationalized in terms of the competition between local high-density (HD) and low-density (LD) structures. Their identification often requires designing parameters that are subject to human intervention. Herein, we use unsupervised learning to discover structures in atomistic simulations of water close to the liquid-liquid critical point (LLCP). Encoding the information on the environment using local descriptors, we do not find evidence for two distinct thermodynamic structures. In contrast, when we deploy nonlocal descriptors that probe instead heterogeneities on the nanometer length scale, this leads to the emergence of LD and HD domains rationalizing the microscopic origins of the density fluctuations close to criticality.

A multidimensional examination of phase separation in single-component fluids

A thermodynamic instability in a homogeneous fluid can lead to spontaneous formation of distinct domains within the fluid. This process involves not only the spatial redistribution of fluid density but also transient exchanges of pressure, temperature, and energy. However, classical theoretical frameworks, such as the Ginzburg–Landau and Cahn–Hilliard models, lack incorporation of these essential thermodynamic aspects. To investigate the dynamics of multiple physical fields during phase separation, we numerically solve a two-dimensional van der Waals fluid model. Thermodynamic consistency is demonstrated by verifying the coexistence curve. While the equilibrium pressure remains similar across the unstable region of the isotherm, we demonstrate that the energy in the system depends on the initial density. Although the majority of energy is stored as heat at typical values of the heat capacity, high-density domains contain less specific energy compared to their low-density counterparts due to interparticle attraction. Consequently, the transition of low-density domains into high-density through the process of coalescence releases excess energy, which redistributes in the form of longitudinal waves and heat. We also highlight the role of parameters, such as heat capacity and thermal conductivity, in less intuitive phenomena, including elevated temperature fluctuations and memory preservation.

Automated Image Analysis of Transmission Electron Micrographs: Nanoscale Evaluation of Radiation-Induced DNA Damage in the Context of Chromatin.

Heavy ion irradiation (IR) with high-linear energy transfer (LET) is characterized by a unique depth dose distribution and increased biological effectiveness. Following high-LET IR, localized energy deposition along the particle trajectories induces clustered DNA lesions, leading to low electron density domains (LEDDs). To investigate the spatiotemporal dynamics of DNA repair and chromatin remodeling, we established the automated image analysis of transmission electron micrographs. Human fibroblasts were irradiated with high-LET carbon ions or low-LET photons. At 0.1 h, 0.5 h, 5 h, and 24 h post-IR, nanoparticle-labeled repair factors (53BP1, pKu70, pKu80, DNA-PKcs) were visualized using transmission electron microscopy in interphase nuclei to monitor the formation and repair of DNA damage in the chromatin ultrastructure. Using AI-based software tools, advanced image analysis techniques were established to assess the DNA damage pattern following low-LET versus high-LET IR. Low-LET IR induced single DNA lesions throughout the nucleus, and most DNA double-strand breaks (DSBs) were efficiently rejoined with no visible chromatin decondensation. High-LET IR induced clustered DNA damage concentrated along the particle trajectories, resulting in circumscribed LEDDs. Automated image analysis was used to determine the exact number of differently sized nanoparticles, their distance from one another, and their precise location within the micrographs (based on size, shape, and density). Chromatin densities were determined from grayscale features, and nanoparticles were automatically assigned to euchromatin or heterochromatin. High-LET IR-induced LEDDs were delineated using automated segmentation, and the spatial distribution of nanoparticles in relation to segmented LEDDs was determined. The results of our image analysis suggest that high-LET IR induces chromatin relaxation along particle trajectories, enabling the critical repair of successive DNA damage. Following exposure to different radiation qualities, automated image analysis of nanoparticle-labeled DNA repair proteins in the chromatin ultrastructure enables precise characterization of specific DNA damage patterns.

Surface tension coupled non-uniformly imposed flows modulate the activity of reproducing chemotactic bacteria in porous media

This paper investigates a non-homogeneous two-dimensional model for reproducing chemotactic bacteria, immersed in a porous medium that experiences non-uniformly imposed flows. It is shown that independently of the form of the fluid velocity field, the compressible/incompressible nature of the fluid significantly shifts the Turing stability-instability transition line. In dry media, Gaussian perturbations travel faster than the hyperbolic secant ones, yet the latter exhibit better stability properties. The system becomes highly unstable under strong flows and high surface tension. Approximated solutions recovered by injecting Gaussian perturbations overgrow, in addition to triggering concentric breathing features that split the medium into high and low-density domains. Secant perturbations on the other hand scatter slowly and form patterns of non-uniformly distributed peaks for strong flows and high surface tension. These results emphasize that Gaussian perturbations strongly modulate the activity of bacteria, hence can be exploited to perform fast spreading in environments with changing properties. In this sense, Gaussian profiles are better candidates to explain quick bacterial responses to external factors. Secant-type approximated solutions slowly modulate the bacterial activity, hence are better alternatives to dive into weak bacterial progressions in heterogeneous media.

81 - Improvement of methacrylate-based polymer networks by introduction of catechol moieties

Dental adhesives mainly consist of methacrylate-based monomers as well as solvents and initiators. The bonding mechanism is based on the penetration of adhesive resins into the demineralized dentin surface and formation of interlocking with exposed collagen fibrils. However, phase separation into hydrophilic/hydrophobic domains leads to water sorption and deterioration of mechanical properties. Furthermore, the esterases and matrix metalloproteinases (MMPs) present in oral environment contribute to methacrylate hydrolysis and collagen degradation, respectively. All these factors accelerate decay along the adhesive interface and cause sub-optimal longevity of the resin filling. A bio-inspired moiety, catechol, has been found to form strong bidentate hydrogen bonds with a variety of surfaces. The purpose of the present study was to design a novel bio-inspired adhesive with catechol moieties and evaluate whether catechol can reduce the heterogeneity of methacrylate-based network structure, decrease water sorption, inhibit the enzyme activities, and improve the longevity of adhesive materials. Catechol methacrylate was synthesized by Steglich esterification which is described in the previous literature. The control adhesive formulations include urethane dimethacrylate (UDMA) as crosslinker (50 wt%), 2-hydroxyethyl methacrylate (HEMA) as monomer (50 wt%), and additional 0.5 wt% 2,2-Dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator. In the novel catechol-contained adhesive, 25 wt% of the HEMA was replaced by catechol methacrylate, with the other components unchanged. To evaluate the performance of these two formulations, dynamic mechanical analysis (DMA), Fourier-transform infrared spectroscopy (FT-IR), water sorption and enzyme (esterases) degradation were conducted to characterize the performance. The novel catechol-contained adhesive showed similar photopolymerization kinetics (final conversion and maximum polymerization rate) to the control one, although multiple works showed that catechol exerts an inhibitory effect on the radial photopolymerization. The water sorption of the novel adhesive, however, was nearly 50% lower than the control adhesive. Moreover, the catechol-contained adhesive showed a higher resistance of the esterase hydrolysis, with less weight loss and lower release of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MMA). The addition of catechol to adhesive formulations reduces the water sorption and improves the resistance of enzyme degradation of methacrylate. These might contribute to the formation of extra hydrogen bonding of catechol in the low-density domains and the inhibitory behaviors of catechol to esterases. Introducing catechol into dental adhesive formulations provides a promising way to enhance the long-term performance of dental adhesive materials. Cytotoxicity and micro-tensile bonding strength tests are essential for the future works.

Baryon-Antibaryon Annihilation in the Evolution of Antimatter Domains in Baryon-Asymmetric Universe

Non-trivial baryosynthesis scenarios can lead to the existence of antimatter domains in a baryon-asymmetrical Universe. The consequences of antibaryon-baryon annihilation at the border of antimatter domains is investigated. Low-density antimatter domains are further classified according to the boundary interactions. A similar classification scheme is also proposed for higher-densities antimatter domains. The antiproton-proton annihilation interactions are therefore schematized and evaluated. The antinuclei-nuclei-interaction patterns are investigated. The two-point correlation functions for antimatter domains are studied in the case of baryon-antibaryon boundary interactions, which influence the space and time evolution. The space-time evolution of antimatter domains after the photon thermalization epoch is analyzed.

Lithospheric density structure of the southern Central Andes constrained by 3D data-integrative gravity modelling

The southern Central Andes (SCA) (between 27° S and 40° S) is bordered to the west by the convergent margin between the continental South American Plate and the oceanic Nazca Plate. The subduction angle along this margin is variable, as is the deformation of the upper plate. Between 33° S and 35° S, the subduction angle of the Nazca plate increases from sub-horizontal (< 5°) in the north to relatively steep (~ 30°) in the south. The SCA contain inherited lithological and structural heterogeneities within the crust that have been reactivated and overprinted since the onset of subduction and associated Cenozoic deformation within the Andean orogen. The distribution of the deformation within the SCA has often been attributed to the variations in the subduction angle and the reactivation of these inherited heterogeneities. However, the possible influence that the thickness and composition of the continental crust have had on both short-term and long-term deformation of the SCA is yet to be thoroughly investigated. For our investigations, we have derived density distributions and thicknesses for various layers that make up the lithosphere and evaluated their relationships with tectonic events that occurred over the history of the Andean orogeny and, in particular, investigated the short- and long-term nature of the present-day deformation processes. We established a 3D model of lithosphere beneath the orogen and its foreland (29° S–39° S) that is consistent with currently available geological and geophysical data, including the gravity data. The modelled crustal configuration and density distribution reveal spatial relationships with different tectonic domains: the crystalline crust in the orogen (the magmatic arc and the main orogenic wedge) is thicker (~ 55 km) and less dense (~ 2900 kg/m3) than in the forearc (~ 35 km, ~ 2975 kg/m3) and foreland (~ 30 km, ~ 3000 kg/m3). Crustal thickening in the orogen probably occurred as a result of stacking of low-density domains, while density and thickness variations beneath the forearc and foreland most likely reflect differences in the tectonic evolution of each area following crustal accretion. No clear spatial relationship exists between the density distribution within the lithosphere and previously proposed boundaries of crustal terranes accreted during the early Paleozoic. Areas with ongoing deformation show a spatial correlation with those areas that have the highest topographic gradients and where there are abrupt changes in the average crustal-density contrast. This suggests that the short-term deformation within the interior of the Andean orogen and its foreland is fundamentally influenced by the crustal composition and the relative thickness of different crustal layers. A thicker, denser, and potentially stronger lithosphere beneath the northern part of the SCA foreland is interpreted to have favoured a strong coupling between the Nazca and South American plates, facilitating the development of a sub-horizontal slab.

Experimental observation of the liquid-liquid transition in bulk supercooled water under pressure.

We prepared bulk samples of supercooled liquid water under pressure by isochoric heating of high-density amorphous ice to temperatures of 205 ± 10 kelvin, using an infrared femtosecond laser. Because the sample density is preserved during the ultrafast heating, we could estimate an initial internal pressure of 2.5 to 3.5 kilobar in the high-density liquid phase. After heating, the sample expanded rapidly, and we captured the resulting decompression process with femtosecond x-ray laser pulses at different pump-probe delay times. A discontinuous structural change occurred in which low-density liquid domains appeared and grew on time scales between 20 nanoseconds to 3 microseconds, whereas crystallization occurs on time scales of 3 to 50 microseconds. The dynamics of the two processes being separated by more than one order of magnitude provides support for a liquid-liquid transition in bulk supercooled water.

Liquid-liquid transitions under pressure

Water Phases Theoretical simulations suggest that deeply supercooled water undergoes a transition between high- and low-density forms, but this transition is difficult to study experimentally because it occurs under conditions in which ice crystallization is extremely rapid. Kim et al. combined x-ray lasers for rapid structure determination with infrared femtosecond pulses for rapid heating of amorphous ice layers formed at about 200 kelvin. The heating process created high-density liquid water at increased pressures. As the layer expanded and decompressed, low-density liquid domains appeared and grew on time scales between 20 nanoseconds and 3 microseconds, which was much faster than competing ice crystallization. Science , this issue p. [978][1] [1]: /lookup/doi/10.1126/science.abb9385

Molecular Imaging of Cholesterol and Lipid Distributions in Model Membranes.

Over recent decades, lipid membranes have become standard models for examining the biophysics and biochemistry of cell membranes. Interrogation of lipid domains within biomembranes is generally done with fluorescence microscopy via exogenous chemical probes. However, fluorophores have limited partitioning tunability, with the majority segregating into the liquid-disordered phase, and fluorescence only strictly reports on the small percentage of tagged lipids. We present simple, label-free imaging of domain formation in lipid monolayers, with chemical selectivity in unraveling lipid and cholesterol composition in different domain types. Exploiting conventional vibrational contrast in spontaneous Raman imaging, combined with chemometrics analysis, allows for examination of ternary systems containing saturated lipids, unsaturated lipids, and cholesterol. We confirm features commonly observed by fluorescence microscopy and provide a quantitative thermodynamic analysis of cholesterol distribution at the single-monolayer level.

Sphingomyelins and ceramides with VLCPUFAs are excluded from low-density raft-like domains in differentiating spermatogenic cells

Rat spermatogenic cells contain sphingomyelins (SMs) and ceramides (Cers) with very long-chain PUFAs (VLCPUFAs) in nonhydroxylated (n-V) and 2-hydroxylated (h-V) forms. How these atypical species distribute among membrane fractions during differentiation was investigated here using a detergent-free procedure to isolate a small light raft-like low-density fraction and a large heavy fraction, mostly derived from the plasma membrane of spermatocytes, round spermatids, and late spermatids. The light fraction contained cholesterol, glycerophospholipids (GPLs), and SM with the same saturated fatty acids in all three stages. In the heavy fraction, as PUFA increased in the GPL and VLCPUFA in SM from spermatocytes to spermatids, the concentration of cholesterol was also augmented. The heavy fraction had mostly n-V SM in spermatocytes, but accumulated h-V SM and h-V Cer in spermatids. A fraction containing intracellular membranes had less SM and more Cer than the latter, but in both fractions SM and Cer species with h-V increased over species with n-V with differentiation. This accretion of h-V was consistent with the differentiation-dependent expression of fatty acid 2-hydroxylase (Fa2h), as it increased significantly from spermatocytes to spermatids. The non-raft region of the plasma membrane is thus the main target of the dynamic lipid synthesis and remodeling that is involved in germ cell differentiation.

Phase coexistence phenomena in an extreme case of the misanthrope process with open boundaries

The misanthrope process is a class of stochastic interacting particle systems, generalizing the simple exclusion process. It allows each site of the lattice to accommodate more than one particle. We consider a special case of the one-dimensional misanthrope process whose probability distribution is completely equivalent to the ordinary simple exclusion process under the periodic boundary condition. By imposing open boundaries, high- and low-density domains can coexist in the system, which we investigate by Monte Carlo simulations. We examine finite-size corrections of density profiles and correlation functions, when the jump rule for particles is symmetric. Moreover, we study properties of delocalized and localized shocks in the case of the totally asymmetric jump rule. The localized shock slowly moves to its stable position in the bulk.

Micrometer-scale electrical breakdown in high-density fluids with large density fluctuations: Numerical model and experimental assessment.

Experimentally observed electrical breakdown voltages (U(B)) in high-pressure gases and supercritical fluids deviate from classical theories for low-pressure gas discharges, and the underlying breakdown mechanisms for the high-density fluids making the U(B) differ from those in the classical discharges are not yet well understood. In this study, we developed an electrical breakdown model for the high-density fluids taking into account the effects of density fluctuations and ion-enhanced field emission (IEFE). The model is based on the concept that a critical anomaly of the U(B) (local minimum near the critical point) is caused by long mean free electron path leading to a large first Townsend coefficient in locally low-density spatial domains generated by the density fluctuations. Also, a modified Paschen's curve considering the effect of the IEFE on the second Townsend coefficient was used to reproduce the U(B) curve in the high-density fluids. Calculations based on the novel model showed good agreements with the experimentally measured U(B) even near the critical point and it also suggested that the critical anomaly of the U(B) depends on the gap distance. These results indicate that both the density fluctuations and the IEFE have to be considered to comprehend the plasmas in high-density and density-fluctuating fluids.

Interaction of arc magmas with subvolcanic hydrothermal systems: insights from compositions and metasomatic textures of olivine crystals in fresh basalts of Daisen and Mengameyama, Western Honshu, Japan

Abstract Pleistocene basalts from Daisen and Mengameyama in the SW Japan volcanic arc of western Honshu are characterized by an abundance of olivine crystals with Fe-rich rims. At Daisen, these have previously been interpreted to have formed from their host melt by equilibrium crystal fractionation and by disequilibrium fractionation during supercooling. Here we use combined electron probe microanalysis, isotopography, transmission electron microscopy and selected area electron diffraction to show that crystal rims are significantly enriched in aluminium (up to c. 1 wt%) and hydrogen (up to c. 10 000 ppm) hosted in oriented low-density amorphous domains. These domains are interpreted to have formed by melting of deuteric and/or post-deuteric metasomatic alteration minerals upon uptake of older olivine crystals into fresh, initially aphyric host melts up to a few hours prior to eruption. It is argued that uptake of variably altered crystals into initially aphyric or sparsely phyric melts may be a common process at subduction zones, and can account for typical disequilibrium textures displayed by arc magmas erupted in SW Japan and elsewhere. Analyses of the altered crystal cargo in arc volcanic rocks therefore provides an important tool for understanding subvolcanic hydrothermal systems and the interaction of ascending melts with such systems. Supplementary material: Olivine mineral chemistry data from two typical Daisen basalts and one typical Mengameyama basalt, and a figure showing the locations of all focussed ion beam (FIB) sections studied here, are available at http://www.geolsoc.org.uk/SUP18760 .

Physical Mechanisms of Fatigue in Neat Polyamide 6,6

The fatigue durability of polyamide 6,6 has been studied for various maximal stresses. We focus on the identification of the microscopic mechanisms responsible for damaging in fatigue regime. We show that the apparent stiffness, or dynamic modulus, decreases linearly as a function of the logarithm of the number of cycles during fatigue tests, except at the very end of the lifetime, prior to failure. This suggests a progressive, accumulative, and generalized damage in the material. This damage mechanism has been characterized at various scales with electron microscopy and X-ray scattering. These analyses show that low density domains are formed at nanometric scale at the early stages of fatigue. The number and size of these domains increase as a function of the number of cycles, explaining the logarithmic decrease of dynamic modulus. These low density domains become anisotropic and evolve into crazes at the ultimate stages of fatigue. The size distribution, density, and form factor of the defects have been characterized during fatigue. The damaging mechanisms and the different steps of damage are discussed in the context of a recent theoretical model.

Observation of low-density domain in polystyrene under nanosecond pulses in quasi-uniform electric field

Low-density domains (LDDs) developed in polystyrene (PS) samples under nanosecond pulses in a quasi-uniform electric field are observed using an on-line transmission microscope. The test samples are 2 mm in thickness with a cylindrical profile, and immersed in clean transformer oil. The nanosecond pulse is trapezoidal with a pulse width of 10 ns. Images taken by the microscope show that the LDDs always appear in the vicinity of the cone electrode, expand as the pulse number increases, and gradually vanish when the output pulses are stopped, only leaving small voids and cracks in the samples. When the pulses are imposed on the sample again, the LDDs emerge and begin to expand again, and finally lead to bulk breakdown of the samples. The observation of LDDs under this condition gives a support for the pre-breakdown and breakdown model by K. C. Kao when applyied to a nanosecond time scale.

Observation of low-density domain in polystyrene under nanosecond pulses in quasi-uniform electric field

Low-density domains (LDDs) developed in polystyrene (PS) samples under nanosecond pulses in a quasi-uniform electric field are observed using an on-line transmission microscope. The test samples are 2 mm in thickness with a cylindrical profile, and immersed in clean transformer oil. The nanosecond pulse is trapezoidal with a pulse width of 10 ns. Images taken by the microscope show that the LDDs always appear in the vicinity of the cone electrode, expand as the pulse number increases, and gradually vanish when the output pulses are stopped, only leaving small voids and cracks in the samples. When the pulses are imposed on the sample again, the LDDs emerge and begin to expand again, and finally lead to bulk breakdown of the samples. The observation of LDDs under this condition gives a support for the pre-breakdown and breakdown model by K. C. Kao when applyied to a nanosecond time scale.

Microphase formation at a 2D solid-gas phase transition.

Density modulated micro-separated phases (microphases) occur at 2D liquid interfaces in the form of alternating regions of high and low density domains. Brewster angle microscopy (BAM) images demonstrate the existence of microphases in cluster, stripe, and mosaic morphologies at the buried interface between hexane and water with fluoro-alkanol surfactant dissolved in the bulk hexane. At high temperature, the surfactant assembles at the interface in a 2D gaseous state. As the system is cooled additional surfactants condense onto the interface, which undergoes a 2D gas-solid phase transition. Microphase structure is observed within a few degrees of this transition in the form of clusters and labyrinthine stripes. Microphases have been observed previously in a number of other systems; nevertheless, we demonstrate that adsorption transitions at the liquid-liquid interface provide a convenient way to observe a full sequence of temperature-dependent 2D phases, from gas to cluster to stripe to mosaic to inverted stripe phases, as well as coexistence between some of these microphases. Cracking and fracture of the clusters reveal that they are a solid microphase. Theories of microphases often predict a single length scale for cluster and stripe phases as a result of the competition between an attractive and a repulsive interaction. Our observation that two characteristic length scales are required to describe clusters whose diameter is much larger than the stripe period, combined with the solid nature of the clusters, suggests that a long-range elastic interaction is relevant. These results complement earlier X-ray measurements on the same system.

Three-dimensional geoelectrical model of southern Kamchatka

The magnetotelluric data for the southern part of Kamchatka Peninsula are interpreted in the mode of three-dimensional (3D) model fitting of the invariant characteristics of impedance and tipper matrices. The interpretation yielded the distribution of electric conductivity in the crust and mantle of the Earth. Conductive blocks are revealed in the junction zone of the Kamchatka depression and Pribrezhnyi horst, as well as beneath the Mutnovskii-Vilyuchik and Avacha-Koryak groups of volcanoes. These blocks are confined to the sublatitudinally trending regional faults and to the upper part of the asthenosphere. The locations of the conductive zones are correlated to the distributions of low-density and low-velocity domains and areas of high seismic and volcanic activity, which is probably due to the significant fluid saturation of these zones.