Search Results (20)

Lipid-based nanomedicines are already widely used in antitumor therapy and gene delivery. However, their complex structural features demand advanced mesoscopic structural characterization tools for effective research and development (R&D) and quality control. Synchrotron small-angle X-ray scattering (SAXS) is a powerful, non-invasive technique for probing nanoscale membrane organizations, monitoring in situ dynamic membrane assembly, and exploring the interactions of components in lipid-based drug delivery systems, including liposomes, lipoplexes, lipid nanoparticles (LNPs), and lyotropic liquid crystals (LLCs). Recent advances in high-flux synchrotron facilities, high-frequency detectors, and automated SAXS data processing pipelines permit a detailed structural characterization of lamellarity, bilayer spacing, internal phases, core–shell morphology, as well as “pump-probe” dynamic process studies for lipid nanomedicines. Though major challenges remain in sample polydispersity and model fitting, the advances in time-resolved synchrotron SAXS, high-throughput automation, and artificial intelligence (AI)-assisted modeling are rapidly reducing this barrier. This review summarizes SAXS methodology and introduces representative case studies in the field of lipid nanomedicines. The performance of BioSAXS beamline BL19U2 in the Shanghai synchrotron radiation facility (SSRF) and prospects of AI-guided drug screening at BL19U2 are highlighted to advance intelligent R&D and quality control for lipid nanomedicines. Full article

In situ physical coal fracturing is one of the key technologies for deep coal resource extraction, among which the liquid nitrogen cyclic freeze–thaw (LNCFT) technique demonstrates remarkable fracturing effects and promising application potential in physical coal breaking. To determine economically viable mining and coalbed methane (CBM) extraction cycles, this study builds on previous research and conducts a series of experiments to investigate the effects of different cold condition temperatures and freeze–thaw cycles on the mesoscopic surface structure and macroscopic mechanical properties of deep, water-rich coal-rock samples. A statistical damage constitutive model for saturated coal-rock under coupled freeze–thaw and loading, incorporating a damage threshold, was established to more accurately describe the damage patterns and mechanisms. The results indicate that lower cold condition temperatures lead to greater mesoscopic crack propagation, lower uniaxial compressive strength, and significantly reduced freeze–thaw failure cycles. Under −45 °C, saturated coal-rock samples experienced macroscopic failure after only 23 freeze–thaw cycles, which is 9 and 15 cycles fewer than those under −30 °C and −15 °C, respectively. Furthermore, measurements of wave velocities in three directions before and after testing revealed that freeze–thaw cycles caused particularly pronounced damage in the direction perpendicular to the bedding planes. Additionally, the established coupled statistical damage constitutive model provides a more accurate and intuitive analysis of the entire process from damage to failure under different cold conditions, showing that as the temperature decreases and freeze–thaw cycles increase, the coal-rock’s brittleness diminishes while plastic deformation and ductile failure characteristics are enhanced. In summary, for coal and CBM extraction using the LNCFT technique, it is recommended to extract gas once after approximately 35 cycles of liquid nitrogen injection. This study provides a theoretical basis for the application of liquid nitrogen cyclic freeze–thaw technology in deep coal fracturing. Full article

Liquid spontaneously spreads on rough lyophilic surfaces, and this is driven by capillarity and defined as capillary wicking. Extensive studies on microtextured surfaces have been applied to microfluidics and their corresponding manufacturing. However, the imbibition at mesoscale roughness has seldom been studied due to lacking fabrication techniques. Inspired by the South American pitcher plant Heliamphora minor, which wicks water on its pubescent inside wall for lubrication and drainage, we implemented 3D printing to fabricate a mimetic mesoscopic trichomes array and investigated the high-flux capillary wicking process. Unlike a uniformly thick climbing film on a microtextured surface, the interval filling of millimeter-long and submillimeter-pitched trichomes creates a film of non-uniform thickness. Different from the viscous dissipation that dominated the spreading on microtextured surfaces, we unveiled an inertia-dominated transition regime with mesoscopic wicking dynamics and constructed a scaling law such that the height grows to 2/3 the power of time for various conditions. Finally, we examined the mass transportation inside the non-uniformly thick film, mimicking a plant nutrition supply method, and realized an open system siphon in the film, with the flux saturation condition experimentally determined. This work explores capillary wicking in mesoscopic structures and has potential applications in the design of low-cost high-flux open fluidics. Full article

We pursue to illustrate the capabilities of the Dual Model of Liquids (DML) showing that it may explain crossed effects notable in Non-Equilibrium Thermodynamics (NET). The aim of the paper is to demonstrate that the DML may correctly model the thermodiffusion, in particular getting formal expressions for positive and negative Soret coefficient, and another “unexpected” mechano-thermal effect recently discovered in liquids submitted to shear strain, for which the first-ever theoretical interpretation is provided. Both applications of the DML are supported by the comparison with experimental data. The phenomenology of liquids, either pure or mixtures, submitted to external force fields is characterized by coupled effects, for instance mechano-thermal and thermo-mechanical effects, depending on whether the application of a mechanical force field generates a coupled thermal effect in the liquid sample or vice-versa. Although these phenomena have been studied since their discoveries, dating back to the XIX century, no firm theoretical interpretation exists yet. Very recently the mesoscopic model of liquids DML has been proposed and its validity and applicability demonstrated in several cases. According to DML, liquids are arranged on a mesoscopic scale by means of aggregates of molecules, or liquid particles. These structures share the liquid world with a population of lattice particles, i.e., elastic waves that interact with the liquid particles by means of an inertial force, allowing the mutual exchange of energy and momentum between the two populations. The hit particle relaxes the acquired energy and momentum due to the interaction, giving them back to the system a step forward and a time-lapse later, alike in a tunnel effect. Full article

The spontaneous formation of self-sorted columnar structures of electron-donating and accepting π-conjugated molecules is attractive for photoconducting and photovoltaic properties. However, the simple mixing of donor–acceptor discotic molecules usually results in the formation of mixed-stacked or alternating-stacked columns. As a new strategy for overcoming this problem, here, we report the “side-chain labeling” approach using binary discotic systems and realize the preferential formation of such self-sorted columnar structures in a thermodynamically stable phase. The demonstrated key strategy involves the use of hydrophobic and hydrophilic side chains. The prepared blend is composed of liquid crystalline phthalocyanine with branched alkyl chains (H₂Pc) and perylenediimide (PDI) carrying alkyl chains at one side and triethyleneglycol (TEG) chains at the other side (PDI_C12/TEG). To avoid the thermodynamically unfavorable contact among hydrophobic and hydrophilic chains, PDI_C12/TEG self-assembles to stack up on top of each other and H₂Pc as well, forming a homo-stacked pair of columns (self-sort). Importantly, H₂Pc and PDI_C12/TEG in the blend are macroscopically miscible and uniform, and mesoscopically segregated. The columnar liquid crystalline microdomains of H₂Pc and PDI_C12/TEG are homeotropically aligned in a glass sandwiched cell. The “labeling” strategy demonstrated here is potentially applicable to any binary discotic system and enables the preferential formation of self-sorted columnar structures. Full article

Ion-flow-stimulated roughening transition is a phenomenon that may prove useful in the hierarchical structuring of nanostructures. In this work, we have investigated theoretically and experimentally the surface texturing of single-crystal and multi-crystalline silicon wafers irradiated using ion-beam flows. In contrast to previous studies, ions had relatively low energies, whereas flow densities were high enough to induce a quasi-liquid state in the upper silicon layers. The resulting surface modifications reduced the wafer light reflectance to values characteristic of black silicon, widely used in solar energetics. Features of nanostructures on different faces of silicon single crystals were studied numerically based on the mesoscopic Monte Carlo model. We established that the formation of nano-pyramids, ridges, and twisting dune-like structures is due to the stimulated roughening transition effect. The aforementioned variety of modified surface morphologies arises due to the fact that the effects of stimulated surface diffusion of atoms and re-deposition of free atoms on the wafer surface from the near-surface region are manifested to different degrees on different Si faces. It is these two factors that determine the selection of the allowable “trajectories” (evolution paths) of the thermodynamic system along which its Helmholtz free energy, F, decreases, concomitant with an increase in the surface area of the wafer and the corresponding changes in its internal energy,$U$ ($dU>0$), and entropy,$S$ ($dS>0$), so that $dF=dU – TdS<0$, where $T$ is the absolute temperature. The basic theoretical concepts developed were confirmed in experimental studies, the results of which showed that our method could produce, abundantly, black silicon wafers in an environmentally friendly manner compared to traditional chemical etching. Full article

In this paper we discuss the effects of modelling and computer simulation activities in promoting student use of lines of reasoning useful to explain proposed or observed situations. The activities are part of a structured Teaching/Learning Sequence on surface phenomena in liquids. We outline a model of liquid based on a mesoscopic approach, examples of computer simulations students can use during the activities, and we describe the Teaching/Learning Sequence. During the pedagogical activities, students can simulate the liquid behaviour by controlling many simulation parameters, such as the interaction intensity among liquid and solid particles. The results of the analysis of student answers to a questionnaire before and after instruction, and of other qualitative data, show that these activities can help the students to think in terms of “mechanisms of functioning”. Full article

In this paper, we proceed to illustrate the consequences and implications of the Dual Model of Liquids (DML) by applying it to the heat propagation. Within the frame of the DML, propagation of thermal (elastic) energy in liquids is due to wave-packet propagation and to the wave-packets’ interaction with the material particles of the liquid, meant in the DML as aggregates of molecules swimming in an ocean of amorphous liquid. The liquid particles interact with the lattice particles, a population of elastic wave-packets, by means of an inertial force, exchanging energy and momentum with them. The hit particle relaxes at the end of the interaction, releasing the energy and momentum back to the system a step forward and a time lapse later, like in a tunnel effect. The tunnel effect and the duality of liquids are the new elements that suggest on a physical basis for the first time, using a hyperbolic equation to describe the propagation of energy associated to the dynamics of wave-packet interaction with liquid particles. Although quantitatively relevant only in the transient phase, the additional term characterizing the hyperbolic equation, usually named the “memory term”, is physically present also once the stationary state is attained; it is responsible for dissipation in liquids and provides a finite propagation velocity for wave-packet avalanches responsible in the DML for the heat conduction. The consequences of this physical interpretation of the “memory” term added to the Fourier law for the phononic contribution are discussed and compiled with numerical prediction for the value of the memory term and with the conclusions of other works on the same topic. Full article

The application of fractional calculus in the field of kinetic theory begins with questions raised by Bernoulli, Clausius, and Maxwell about the motion of molecules in gases and liquids. Causality, locality, and determinism underly the early work, which led to the development of statistical mechanics by Boltzmann, Gibbs, Enskog, and Chapman. However, memory and nonlocality influence the future course of molecular interactions (e.g., persistence of velocity and inelastic collisions); hence, modifications to the thermodynamic equations of state, the non-equilibrium transport equations, and the dynamics of phase transitions are needed to explain experimental measurements. In these situations, the inclusion of space- and time-fractional derivatives within the context of the continuous time random walk (CTRW) model of diffusion encodes particle jumps and trapping. Thus, we anticipate using fractional calculus to extend the classical equations of diffusion. The solutions obtained illuminate the structure and dynamics of the materials (gases and liquids) at the molecular, mesoscopic, and macroscopic time/length scales. The development of these models requires building connections between kinetic theory, physical chemistry, and applied mathematics. In this paper, we focus on the kinetic theory of gases and liquids, with particular emphasis on descriptions of phase transitions, inter-phase mixing, and the transport of mass, momentum, and energy. As an example, we combine the pressure–temperature phase diagrams of simple molecules with the corresponding anomalous diffusion phase diagram of fractional calculus. The overlap suggests links between sub- and super-diffusion and molecular motion in the liquid and the vapor phases. Full article

Densely grafted comb-like macromolecules (bottlebrushes) with alternating solvophobic and solvophilic side chains were studied in a selective solvent and at the liquid interface using mesoscopic computer simulations. The effects of backbone length and copolymer composition were considered. While self-assembly in solution revealed only spherical aggregates for all ar-chitectures studied, adsorption onto the liquid interface in particular cases resulted in morpho-logical changes, with worm-like aggregates or a continuous monolayer observed. In turn, the compression of macromolecules at the interface also leads to morphological transitions, includ-ing the formation of a mesh-like percolated structure. The obtained results may be useful for the preparation of solid nanoparticles of anisotropic shape or nanostructured ultra-thin copolymer films. Full article

Liquid-liquid phase separation underlies the formation of membrane-less organelles inside living cells. The mechanism of this process can be examined using simple aqueous mixtures of two or more solutes, which are able to phase separate at specific concentration thresholds. This work presents the first experimental evidence that mesoscopic changes precede visually detected macroscopic phase separation in aqueous mixtures of two polymers and a single polymer and salt. Dynamic light scattering (DLS) analysis indicates the formation of mesoscopic polymer agglomerates in these systems. These agglomerates increase in size with increasing polymer concentrations prior to visual phase separation. Such mesoscopic changes are paralleled by changes in water structure as evidenced by Attenuated Total Reflection—Fourier Transform Infrared (ATR-FTIR) spectroscopic analysis of OH-stretch bands. Through OH-stretch band analysis, we obtain quantitative estimates of the relative fractions of four subpopulations of water structures coexisting in aqueous solutions. These estimates indicate that abrupt changes in hydrogen bond arrangement take place at concentrations below the threshold of macroscopic phase separation. We used these experimental observations to develop a model of phase separation in aqueous media. Full article

Mesoscopic shear elasticity has been revealed in ordinary liquids both experimentally by reinforcing the liquid/surface interfacial energy and theoretically by nonextensive models. The elastic effects are here examined in the frame of small molecules with strong electrostatic interactions such as room temperature ionic liquids [emim][Tf2N] and nitrate solutions exhibiting paramagnetic properties. We first show that these charged fluids also exhibit a nonzero low-frequency shear elasticity at the submillimeter scale, highlighting their resistance to shear stress. A neutron scattering study completes the dynamic mechanical analysis of the paramagnetic nitrate solution, evidencing that the magnetic properties do not induce the formation of a structure in the solution. We conclude that the elastic correlations contained in liquids usually considered as viscous away from any phase transition contribute in an effective way to collective effects under external stress whether mechanical or magnetic fields. Full article

In this brief review, we give an introduction to selected colloidal and microfluidic nematic microstructures, as enabled by the inherent anisotropy and microscopic orientational ordering in complex liquid crystalline materials. We give a brief overview of the mesoscopic theory, for equilibrium and dynamics, of nematic fluids, that provides the framework for understanding, characterization, and even prediction of such microstructures, with particular comment also on the role of topology and topological defects. Three types of nematic microstructures are highlighted: stable or metastable structures in nematic colloids based on spherical colloidal particles, stationary nematic microfluidic structures, and ferromagnetic liquid crystal structures based on magnetic colloidal particles. Finally, this paper is in honor of Noel A. Clark, as one of the world pioneers that helped to shape this field of complex and functional soft matter, contributing at different levels to works of various groups worldwide, including ours. Full article

Proteins with low complexity, disordered sequences are receiving increasing attention due to their central roles in the biogenesis and regulation of membraneless organelles. In eukaryotic organisms, a substantial fraction of disordered proteins reside in the nucleus, thereby facilitating the formation of nuclear bodies, nucleolus, and chromatin compartmentalization. The heterochromatin family of proteins (HP1) is an important player in driving the formation of gene silenced mesoscopic heterochromatin B compartments and pericentric regions. Recent experiments have shown that the HP1a sequence of Drosophila melanogaster can undergo liquid-liquid phase separation under both in vitro and in vivo conditions, induced by changes of the monovalent salt concentration. While the phase separation of HP1a is thought to be the mechanism underlying chromatin compartmentalization, the molecular level mechanistic picture of salt-driven phase separation of HP1a has remained poorly understood. The disordered hinge region of HP1a is seen as the driver of salt-induced condensation because of its charge enriched sequence and post-translational modifications. Here, we set out to decipher the mechanisms of salt-induced condensation of HP1a through a systematic study of salt-dependent conformations of single chains and fuzzy dimers of disordered HP1a hinge sequences. Using multiple independent all-atom simulations with and without enhanced sampling, we carry out detailed characterization of conformational ensembles of disordered HP1a chains under different ionic conditions using various polymeric and structural measures. We show that the mobile ion release, enhancement of local transient secondary structural elements, and side-chain exposure to solvent are robust trends that accompany fuzzy dimer formation. Furthermore, we find that salt-induced changes in the ensemble of conformations of HP1a disordered hinge sequence fine-tune the inter-chain vs. self-chain interactions in ways that favor fuzzy dimer formation under low salt conditions in the agreement with condensation trends seen in experiments. Full article

Fluid flow between adjacent tracheids is realized through bordered pits in the xylem of conifers. The pit has an extremely small size and a highly complex structure. This paper presents a mesoscopic analytical method for the relationship between the pit structure and its hydraulic characteristics through mathematical modeling using the lattice Boltzmann method (LBM) and curved boundary treatment. Mongolian Scots pine were selected as the research subject of this study, and the bordered pit structure parameters was collected by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the original geometric features were maintained for direct modeling analysis. The model revealed the relationship between various components of the bordered pit and liquid flow velocity/resistance, indicating that margo is the main factor affecting flow resistance. Further anatomical investigation separately analyzed the influence of change in a single factor, including pit diameter, pit aperture diameter, pit depth, torus diameter, and margo thickness, on the overall flow and pressure drop to confirm the importance of various factors in this relationship. Additionally, the influence of pore size and pore location distribution in the margo on the flow rate and pressure drop was further analyzed quantitatively. The results showed that the flow rate through individual pores is the result of the combined effect of pore area and radial position of the pore in the margo. Our study promotes the research and application of the mesoscopic model LBM in simulating flow conditions in the complex flow field of pits, which realizes the numerical analysis of the flow field model based on individualized real bordered pits. In comparison with the classical macroscopic model, the accuracy and effectiveness of the proposed model are proved. This research can provide a promising method for analyzing the physiological and ecological functions of conifer and realizing the efficient utilization of wood resources. Full article