Anisotropic-Isotropic Transition of Cages at the Glass Transition.

Characterizing the local structural evolution is an essential step in understanding the nature of glass transition. In this work, we probe the evolution of Voronoi cell geometry in simple glass models by simulations and colloid experiments, and find that the individual particle cages deform anisotropically in supercooled liquid and isotropically in glass. We introduce an anisotropy parameter k for each Voronoi cell, whose mean value exhibits a sharp change at the mode-coupling glass transition ϕ_{c}. Moreover, a power law of packing fraction ϕ∝q_{1}^{d} is discovered in the supercooled liquid regime with d>D, in contrast to d=D in the glass regime, where q_{1} is the first peak position of structure factor, and D is the space dimension. This power law is qualitatively explained by the change of k. The active motions in supercooled liquid are spatially correlated with long axes rather than short axes of Voronoi cells. In addition, the dynamic slowing down approaching the glass transition can be well characterized through a modified free-volume model based on k. These findings reveal that the structural parameter k is effective in identifying the structure-dynamics correlations and the glass transition in these systems.

Shear-assisted grain coarsening in colloidal polycrystals.

Grain growth under shear annealing is crucial for controlling the properties of polycrystalline materials. However, their microscopic kinetics are not well understood because individual atomic trajectories are difficult to track. Here, we study grain growth with single-particle kinetics in colloidal polycrystals using video microscopy. Rich grain-growth phenomena are revealed in three shear regimes, including the normal grain growth (NGG) in weak shear melting-recrystallization process in strong shear. For intermediate shear, early stage NGG is arrested by built-up stress and eventually gives way to dynamic abnormal grain growth (DAGG). We find that DAGG occurs via a melting-recrystallization process, which naturally explains the puzzling stress drop at the onset of DAGG in metals. Moreover, we visualize that grain boundary (GB) migration is coupled with shear via disconnection gliding. The disconnection-gliding dynamics and the collective motions of ambient particles are resolved. We also observed that grain rotation can violate the conventional relation [Formula: see text] (R is the grain radius, and θ is the misorientation angle between two grains) by emission and annihilation of dislocations across the grain, resulting in a step-by-step rotation. Besides grain growth, we discover a result in shear-induced melting: The melting volume fraction varies sinusoidally on the angle mismatch between the triangular lattice orientation of the grain and the shear direction. These discoveries hold potential to inform microstructure engineering of polycrystalline materials.

Morphologies and dynamics of free surfaces of crystals composed of active particles.

Active matter exhibits various collective motions and nonequilibrium phases, such as crystals; however, their surface properties have been poorly explored. Here, we use Brownian dynamics simulations to investigate the surface morphology and dynamics of two-dimensional active crystals during and after growth. For crystal growth on a substrate, the position and roughness of the crystal surface reach steady states at different times. In the steady state, the surface exhibits superdiffusive behaviour at the short time, and the roughness is insensitive to the roughening process and particle activity. We observe two-stage and three-stage surface roughening at different Péclet numbers. The result of dynamic scaling analysis shows that the surface is similar to anomalous roughening, which is distinct from the normal roughening typically found in conventional passive systems. Capillary wave theory for a thermal equilibrium system can describe the active surface fluctuations only in the long-wavelength regime, indicating that active particles mainly drive the surface out of equilibrium locally. These similarities and differences between the active and passive crystal surfaces are essential for understanding active crystals and interfaces.

Modes of surface premelting in colloidal crystals composed of attractive particles.

Crystal surfaces typically melt into a thin liquid layer at temperatures slightly below the melting point of the crystal. Such surface premelting is prevalent in all classes of solids and is important in a variety of metallurgical, geological and meteorological phenomena. Premelting has been studied using X-ray diffraction and differential scanning calorimetry, but the lack of single-particle resolution makes it hard to elucidate the underlying mechanisms. Colloids are good model systems for studying phase transitions because the thermal motions of individual micrometre-sized particles can be tracked directly using optical microscopy. Here we use colloidal spheres with tunable attractions to form equilibrium crystal-vapour interfaces, and study their surface premelting behaviour at the single-particle level. We find that monolayer colloidal crystals exhibit incomplete premelting at their perimeter, with a constant liquid-layer thickness. In contrast, two- and three-layer crystals exhibit conventional complete melting, with the thickness of the surface liquid diverging as the melting point is approached. The microstructures of the surface liquids differ in certain aspects from what would be predicted by conventional premelting theories. Incomplete premelting in the monolayer crystals is triggered by a bulk isostructural solid-solid transition and truncated by a mechanical instability that separately induces homogeneous melting within the bulk. This finding is in contrast to the conventional assumption that two-dimensional crystals melt heterogeneously from their free surfaces (that is, at the solid-vapour interface). The unexpected bulk melting that we observe for the monolayer crystals is accompanied by the formation of grain boundaries, which supports a previously proposed grain-boundary-mediated two-dimensional melting theory. The observed interplay between surface premelting, bulk melting and solid-solid transitions challenges existing theories of surface premelting and two-dimensional melting.

Association between periprocedural myocardial injury and long-term all-cause mortality in patients undergoing transcatheter aortic valve replacement: a systematic review and meta-analysis.

Objective. The purpose of this meta-analysis was to investigate the effect of periprocedural myocardial injury (PPMI) on long-term all-cause mortality in patients undergoing transcatheter aortic valve replacement (TAVR) and to explore potential factors associated with mortality risk. Design. The PubMed, Embase, and Cochrane Library databases were searched up to April 2022. Studies reporting the effect of PPMI on the risk of long-term all-cause mortality were included. The summary odds ratio (OR) was calculated using a random effects model. Additionally, meta-regression and subgroup analyses were conducted according to specific research characteristics to explore sources of heterogeneity. Results. Fourteen studies involving 6,415 patients who underwent TAVR showed that the occurrence of PPMI was associated with a higher risk of long-term mortality. Subgroup analysis showed that in the group of aged ≥82 years, men accounted for less than 50%, coronary artery disease patients accounted for more than 50%, and the proportion of patients with chronic kidney disease accounted for more than 60%, the proportion of patients with atria fibrillation accounted for less than 30%, and the Society of Thoracic Surgeons predicted risk of mortality score was >8 points, patients with PPMI had higher long-term all-cause mortality than those without PPMI. Conclusions. Among the patients who underwent TAVR, those who developed PPMI had higher long-term all-cause mortality.

Morphologies and dynamics of the interfaces between active and passive phases.

Active matters exhibit interesting collective behaviors and novel phases, which provide an important platform for the study of nonequilibrium physics. Mixtures of active and passive particles have been intensively studied in motility-induced phase separation, but the morphology of the active-passive interface has been poorly explored. In this work, we investigate the interface morphology in two-dimensional mixtures of active and passive particles using Brownian dynamics simulations. By systematically changing the Péclet number (Pe) and area fraction (ρ), we obtain the phase diagram of the active-passive interface, including rough sharp, rough invasive and flat interdiffusive interfaces. For a sharp interface, dynamic scaling analysis in the propagation stage shows that the roughness exponent α, the growth exponent ß, the time exponent κ, and the dynamic exponent z satisfy z = α/(ß - κ). Such anomalous scaling indicates that the roughening behavior does not belong to the conventional universality classes with Family-Vicsek scaling for the growth of passive interfaces. On the other hand, the interface in the middle-wavelength regime during the morphology relaxation stage can be described by capillary wave theory. The mean interface position propagates with time as t1/2, which is robust at different ρ and Pe values in the propagation stage and exhibits superdiffusion in the morphology relaxation stage. These similarities and differences between the active-inactive interfaces and passive interfaces cast light on the interfacial growth of active matter.

Surface roughening, premelting and melting of monolayer and bilayer crystals.

Dimensionality often strongly affects material properties and phase transition behaviors, but its effects on crystal surfaces, such as roughening and premelting, have been poorly studied. Our simulation revealed that these surface behaviors are distinct in monolayer and multilayer Lennard-Jones (LJ) crystals. Solid surfaces fluctuate as capillary waves during the roughening process, but complete roughening is preempted by premelting. As the melting temperature is approached, the thickness of the premelted liquid layer approaches a constant (i.e., blocked premelting) for monolayer crystals, but diverges as a power law (i.e., complete premelting) for bilayer and trilayer crystals. The surface liquids of monolayer crystals contain crystalline patches and exhibits rough liquid-vapour and liquid-crystal interfaces, in contrast to the normal surface liquids of bilayer and trilayer crystals. Monolayer crystals melt heterogeneously from the surface without forming a hexatic phase and produce many vacancies.

Direct Evidence of Void-Induced Structural Relaxations in Colloidal Glass Formers.

Particle dynamics in supercooled liquids are often dominated by stringlike motions in which lines of particles perform activated hops cooperatively. The structural features triggering these motions, crucial in understanding glassy dynamics, remain highly controversial. We experimentally study microscopic particle dynamics in colloidal glass formers at high packing fractions. With a small polydispersity leading to glass-crystal coexistence, a void in the form of a vacancy in the crystal can diffuse reversibly into the glass and further induces stringlike motions. In the glass, a void takes the form of a quasivoid consisting of a few neighboring free volumes and is transported by the stringlike motions it induces. In fully glassy systems with a large polydispersity, similar quasivoid actions are observed. The mobile particles cluster into stringlike or compact geometries, but the compact ones can be further broken down into connected sequences of strings, establishing their general importance.

Melting and solid-solid transitions of two-dimensional crystals composed of Janus spheres.

Colloidal model systems have been extensively used in the studies of various phase transitions, but melting and solid-solid transitions have rarely been explored in monolayer colloidal crystals with anisotropic attractions. Patchy colloidal particles have served as important model systems of atoms and molecules with anisotropic interactions. In this work, we study the melting and solid-solid transitions of two-dimensional crystals composed of Janus colloidal spheres using Langevin dynamics simulation. We discovered a first-order solid-solid transition from a single crystal with uniform stripes to a novel crystal with polycrystalline domains of stripes. The centers of masses of the particles maintain the morphology of a single crystal with long-range translational and bond-orientational orders, but particle orientations form polycrystalline domains of stripes. The stripe domains form by a strain-induced nucleation process via the collective rotation of particles. In addition to this solid-solid transition, the melting transition at a higher temperature follows a two-step Kosterlitz-Thouless-Halperin-Nelson-Young (KTHNY) scenario, similar to most isotropic particle systems.

Green-Light-Triggered Phase Transition of Azobenzene Derivatives toward Reversible Adhesives.

Studies on the azobenzene derivative based phase transitions mostly rely on photoisomerization, which require a long time to spontaneously revert back. Here we show a photothermal-driven solid-to-liquid transition and fast reversion of azobenzene derivatives. Owing to the aggregation of suitably substituted azobenzenes, solid-to-liquid transitions can be induced by photothermal effects under irradiation with green light. The liquid-state azobenzene derivatives spontaneously solidify again within 2 min due to heat release in a purely physical fashion. One thus obtains a perfectly reversible adhesion with a strength as high as that of commercial materials. Our work affords a novel concept to construct reversible adhesives via phase transitions of organic compounds induced by light.

Prognostic value of repeated serum kisspeptin measurements in early first trimester pregnancy: a preliminary study.

RESEARCH QUESTION: What is the diagnostic value of maternal kisspeptin in patients with asymptomatic first-trimester pregnancies, and what is the prognostic significance of kisspeptin versus beta-HCG in early pregnancies. DESIGN: Case-control study in academic medical centres. Patients with no confounding co-morbidities who conceived by IVF and intracytoplasmic sperm injection were analysed. Maternal serum samples were assessed at the time of pregnancy testing. Women who achieved a positive pregnancy test were asked to take serum samples 4 days later. According to the follow-up results, patients who experienced biochemical pregnancy loss (n = 24) and early miscarriage (n = 21), and women who achieved a viable pregnancy (n = 28), were included in this study. Serum samples were collected to detect kisspeptin and beta-HCG, respectively. RESULTS: Single serum determinations of kisspeptin and beta-HCG were correlated with the different pregnancy outcomes. Women who experienced biochemical pregnancy loss showed lower kisspeptin levels than those in groups B and C. No significant difference, however, was observed at the time of pregnancy testing in women who had experienced early miscarriage and those who had achieved viable pregnancy. Sequential measurements of serum kisspeptin are not as effective as beta-HCG in determining pregnancy outcome. Increased kisspeptin level was associated with reduced miscarriage risk. CONCLUSION: Single serum measurement of kisspeptin is significantly altered in pregnant and non-pregnant women. However, it failed to discriminate between miscarriage and ongoing pregnancies in first-trimester pregnancy. Neither single nor sequential kisspeptin have higher diagnostic performance for miscarriage than beta-HCG in early stage.

Transformations of body-centered cubic crystals composed of hard or soft spheres to liquids or face-centered cubic crystals.

The monodispersed hard-sphere system is one of the simplest models for the study of phase transitions. Despite intensive studies of crystallization and melting of hard-sphere face-centered cubic (FCC) crystals, the phase transformations of hard-sphere body-centered cubic (BCC) crystals have not been explored because hard spheres cannot form a stable BCC lattice. In fact, unstable BCC hard-sphere crystals and their related phase transformations can be experimentally achieved. Here, we measured the kinetics of the melting and solid-solid transformations of BCC hard-sphere crystals at various volume fractions via molecular dynamics simulations. When the volume fraction ϕ < 0.494, the system melts catastrophically. At ϕ > 0.545, the BCC crystal transforms to a metastable polycrystal consisting of FCC and hexagonal close-packed (HCP) domains, which is different from those crystallized from supercooled liquids, and then slowly equilibrates toward the FCC crystal. At 0.494 < ϕ < 0.545, the BCC crystal transforms to an intermediate-order metastable state consisting of BCC and non-crystal particles without FCC and HCP symmetries and then equilibrates toward the coexistence of the FCC crystal and liquid. We further studied the melting and BCC-FCC transitions of crystals composed of soft spheres with potential u(r) = ϵ(r/σ)-n . The unstable BCC crystals at n = 12, 9, 8 exhibit similar melting and BCC-FCC transitions as hard-sphere BCC crystals, while the metastable BCC crystals at n = 5, 6, 7 melt quickly at low densities but take very long time for the BCC-FCC transition at high densities. We also estimate the BCC-FCC interfacial energy and critical nucleus size. These results cast light on the melting and solid-solid transformations of atomic BCC crystals, which exist widely in nature.

Homogeneous melting near the superheat limit of hard-sphere crystals.

A defect-free crystal can be superheated into a metastable state above its melting point and eventually melts via homogeneous nucleation. Further increasing the temperature leads to the metastable crystal becoming unstable and melting catastrophically once beyond its superheat limit. The homogeneous melting is not well studied near the superheat limit and this limit is difficult to measure accurately, even for the simplest model of hard-sphere crystals. Here our molecular-dynamics simulations identify its superheat limit at volume fraction φlimit = 0.494 ± 0.003, which is higher than the previous theoretical estimations. We found that the hard-sphere crystal at the superheat limit does not satisfy Born's melting criterion, but has a vanishing bulk modulus, i.e. a spinodal instability, which preempts other thermodynamic or mechanical instabilities. At the strong superheating regime, the nucleation deviates from the assumptions in the classical nucleation theory. In contrast to crystallization which often develops nuclei with various intermediate structures, the melting of face-centered cubic (fcc) hard-sphere crystal does not produce intermediate structures such as body-centered cubic (bcc) crystallites although bcc is more stable than fcc at the strong superheating regime. Moreover, we found that the time evolutions of the order parameters and the pressure all exhibit a compressed exponential function, in contrast to the stretched exponential relaxation of supercooled liquids. The compressed exponential functions have the same exponent, which poses a new challenge to theory.

Expression of NDUFA13 in asthenozoospermia and possible pathogenesis.

Asthenozoospermia is a common cause of male infertility, which is characterized by reduced forward motility of spermatozoa. The cause and pathogenesis of asthenozoospermia are not fully understood. The purpose of this study was to investigate the expression of nicotinamide adenine dinucleotide (NADH) dehydrogenase (ubiquinone) 1 alpha subcomplex, 13 (NDUFA13) in the spermatozoa of men with asthenozoospermia and its possible pathogenesis. Protein content of NDUFA13 in spermatozoa was measured by Western blot analysis. The results showed that NDUFA13 expression in spermatozoa was significantly lower in men with asthenozoospermic than in men with normozoospermia (P < 0.01). Immunofluorescence experiments showed that NDUFA13 was expressed predominantly in the sperm mid-piece. A lower mitochondrial membrane potential, a higher intracellular reactive oxygen species (ROS) level and more apoptotic cells were also detected in men with asthenozoospermia. NDUFA13-specific small interfering RNA was used in the mouse spermatocyte GC2-spd cell line to down-regulate the expression of NDUFA13. The knockdown of NDUFA13 in the GC2-spd cells caused a collapse of mitochondrial membrane potential, an increase in ROS level and more apoptotic cells. Our study showed that NDUFA13 deficiency may be associated with asthenozoospermia through the disturbance of spermatozoa mitochondrial membrane potential and by increasing apoptosis and intracellular ROS.

Colloidal diffusion over a quasicrystalline-patterned surface.

We report a systematic study of colloidal diffusion over a substrate with quasicrystalline-patterned holes. Silica spheres of diameter comparable to the hole diameter diffuse over the patterned substrate and experience a gravitational potential U(x, y). Using optical microscopy, we track the particle trajectories and find two distinct states: a trapped state when the particles are inside the holes and a free-diffusion state when they are on the flat surface outside the holes. The potential U(x, y) and dynamic properties of the diffusing particle, such as its mean dwell time, mean square displacement, and long-time diffusion coefficient DL, are measured simultaneously. The measured DL is in good agreement with the prediction of two theoretical models proposed for diffusion over a quasicrystal lattice. The experiment demonstrates the applications of this newly constructed potential landscape.

Two-step nucleation mechanism in solid-solid phase transitions.

The microscopic kinetics of ubiquitous solid-solid phase transitions remain poorly understood. Here, by using single-particle-resolution video microscopy of colloidal films of diameter-tunable microspheres, we show that transitions between square and triangular lattices occur via a two-step diffusive nucleation pathway involving liquid nuclei. The nucleation pathway is favoured over the direct one-step nucleation because the energy of the solid/liquid interface is lower than that between solid phases. We also observed that nucleation precursors are particle-swapping loops rather than newly generated structural defects, and that coherent and incoherent facets of the evolving nuclei exhibit different energies and growth rates that can markedly alter the nucleation kinetics. Our findings suggest that an intermediate liquid should exist in the nucleation processes of solid-solid transitions of most metals and alloys, and provide guidance for better control of the kinetics of the transition and for future refinements of solid-solid transition theory.

Nonclassical Nucleation in a Solid-Solid Transition of Confined Hard Spheres.

A solid-solid phase transition of colloidal hard spheres confined between two planar hard walls is studied using a combination of molecular dynamics and Monte Carlo simulation. The transition from a solid consisting of five crystalline layers with square symmetry (5□) to a solid consisting of four layers with triangular symmetry (4△) is shown to occur through a nonclassical nucleation mechanism that involves the initial formation of a precritical liquid cluster, within which the cluster of the stable 4△ phase grows. Free-energy calculations show that the transition occurs in one step, crossing a single free-energy barrier, and that the critical nucleus consists of a small 4△ solid cluster wetted by a metastable liquid. In addition, the liquid cluster and the solid cluster are shown to grow at the planar hard walls. We also find that the critical nucleus size increases with supersaturation, which is at odds with classical nucleation theory. The △-solid-like cluster is shown to contain both face-centered-cubic and hexagonal-close-packed ordered particles.

Geometric frustration in buckled colloidal monolayers.

Geometric frustration arises when lattice structure prevents simultaneous minimization of local interaction energies. It leads to highly degenerate ground states and, subsequently, to complex phases of matter, such as water ice, spin ice, and frustrated magnetic materials. Here we report a simple geometrically frustrated system composed of closely packed colloidal spheres confined between parallel walls. Diameter-tunable microgel spheres are self-assembled into a buckled triangular lattice with either up or down displacements, analogous to an antiferromagnetic Ising model on a triangular lattice. Experiment and theory reveal single-particle dynamics governed by in-plane lattice distortions that partially relieve frustration and produce ground states with zigzagging stripes and subextensive entropy, rather than the more random configurations and extensive entropy of the antiferromagnetic Ising model. This tunable soft-matter system provides a means to directly visualize the dynamics of frustration, thermal excitations and defects.

Depressive disorder benefits of cities: Evidence from the China.

BACKGROUND: Rapid urbanization is a major trend in global population migration. There is growing debate about whether this urban-rural disparity exacerbate depression at the individual level. This study aims to investigate how urban living has a beneficial impact on individual mental health. METHODS: Based on the data of 15,764 participants in the 2018 China Health and Retirement Longitudinal Study (CHARLS), we perform analysis of variance to identify the gap in depression levels between urban and rural areas. Extensive comparisons and detailed statistical analyses are carried out to demonstrate the differences in social participation between urban and rural residents. Finally, we conduct a series of mediation and moderation analyses to reveal the underlying mechanisms of depressive disorder benefits of cities. RESULTS: The results indicate that those who lived in urban areas were less likely to suffer from depression (ß = -1.461, 95 % CI = [-1.691, -1.235], p < 0.001). Social engagement is found to mediate the relationship between residence type (ß = 0.164, 95 % CI = [0.136, 0.193], p < 0.001) and individual depression (ß = -0.462, 95 % CI = [-0.587, -0.337], p < 0.001). City size plays a moderating role in the association between urban living and social engagement. LIMITATIONS: The mechanism is conducted through cross-sectional data. Self-reported depression status is accessed in this study, which could lead to measurement error. CONCLUSION: This study demonstrates the beneficial effects of urban living on individual depression, and reveals the mechanism by which urbanization at different scales affects the prevalence of depression.