Condensed Matter

Nanocarriers are nanosized materials commonly used for targeted-oriented delivery of active compounds, including antimicrobials and small-molecular drugs. They equally represent fundamental and engineering challenges since sophisticated nanocarriers must show adequate structure, stability, and function in complex ambients. Here, we report on the computational design of a distinctive class of nanocarriers, built from buckled armored nanodroplets, able to selectively encapsulate or release a probe load under specific flow conditions. Mesoscopic simulations offer detailed insight into the interplay between the characteristics of laden surface coverage and evolution of the droplet morphology. First, we describe in detail the formation of \textit{pocket-like} structures in Pickering emulsion nanodroplets and their stability under external flow. Then we use that knowledge to test the capacity of these emulsion-based pockets to yield flow-assisted encapsulation or expulsion of a probe load. Finally, the rheological properties of our model carrier are put into perspective with those of delivery systems employed in pharmaceutical and cosmetic technology.

Glasses show vibrational properties that are markedly different to those of crystals which are known as phonons. For example, excess low-frequency modes (the so-called boson peak), vibrational localization, and strong scattering of phonons have been the most discussed topics, and a theoretical understanding of these phenomena is challenging. To address this problem, computational simulations are a powerful tool, which have been employed by many previous works. In this chapter, we describe simulation methods for studying the vibrational properties of glasses (and any solid-state materials). We first present a method for studying vibrational eigenmodes. Since vibrational motions of particles are excited along eigenmodes, the eigenmodes are fundamental to descriptions of vibrational properties. The eigenmodes in glasses are non-phonon modes in general, and some of them are even localized in space. We next present a method of analysing phonon transport, which is also crucial for understanding vibrational properties. Since phonons are not eigenmodes in glasses, they are decomposed into several different, non-phonon eigenmodes. As a result, phonons in glasses are strongly scattered. In addition, we describe how to analyse the elastic response. The elastic response of glasses is also anomalous with respect to that of crystals. Finally, we briefly introduce recent advances that have been achieved by means of large-scale computational simulations.

Liquid crystal elastomers/glasses are active materials that can have significant metric change upon stimulation. The local metric change is determined by its director pattern that describes the ordering direction and hence the direction of contraction. We study logarithmic spiral patterns on flat sheets that evolve into cones on deformation, with Gaussian curvature localized at tips. Such surfaces, Gaussian flat except at their tips, can be combined to give compound surfaces with GC concentrated in lines. We characterize all possible metric-compatible interfaces between two spiral patterns, specifically where the same metric change occurs on each side. They are classified as hyperbolic-type, elliptic-type, concentric spiral, and continuous-director interfaces. Upon the cone deformations and additional isometries, the actuated interfaces form creases bearing non-vanishing concentrated Gaussian curvature, which is formulated analytically for all cases and simulated numerically for some examples. Analytical calculations and the simulations agree qualitatively well. Furthermore, the relaxation of Gaussian-curved creases is discussed and cantilevers with Gaussian curvature-enhanced strength are proposed. Taken together, our results provide new insights in the study of curved creases, lines bearing Gaussian curvature, and their mechanics arising in actuated liquid crystal elastomers/glasses, and other related active systems.

Conformation-dependent design of polymer sequences can be considered as a tool to control macromolecular self-assembly. We consider the monomer unit sequences created via the modification of polymers in a homogeneous melt in accordance with the spatial positions of the monomer units. The geometrical patterns of lamellae, hexagonally packed cylinders, and balls arranged in a body-centered cubic lattice are considered as typical microphase-separated morphologies of block copolymers. Random trajectories of polymer chains are described by the diffusion-type equations and, in parallel, simulated in the computer modeling. The probability distributions of block length k , which are analogous to the first-passage probabilities, are calculated analytically and determined from the computer simulations. In any domain, the probability distribution can be described by the asymptote k ??/2 at moderate values of k if the spatial size of the block is less than the smallest characteristic size of the domain. For large blocks, the exponential asymptote exp(?�constk a 2 / d 2 as ) is valid, d as being the asymptotic domain length (a is the monomer unit size). The number average block lengths and their dispersities change linearly with the block length for lamellae, cylinders, and balls, when the domain is characterized by a single characteristic size. If the domain is described by more than one size, the number average block length can grow nonlinearly with the domain sizes and the length das can depend on all of them.

The glass-forming ability is an important material property for manufacturing glasses and understanding the long-standing glass transition problem. Because of the nonequilibrium nature, it is difficult to develop the theory for it. Here we report that the glass-forming ability of binary mixtures of soft particles is related to the equilibrium melting temperatures. Due to the distinction in particle size or stiffness, the two components in a mixture effectively feel different melting temperatures, leading to a melting temperature gap. By varying the particle size, stiffness, and composition over a wide range of pressures, we establish a comprehensive picture for the glass-forming ability, based on our finding of the direct link between the glass-forming ability and the melting temperature gap. Our study reveals and explains the pressure and interaction dependence of the glass-forming ability of model glass-formers, and suggests strategies to optimize the glass-forming ability via the manipulation of particle interactions.

We investigate the mechanical response of packings of purely repulsive, frictionless disks to quasistatic deformations. The deformations include simple shear strain at constant packing fraction and at constant pressure, "polydispersity" strain (in which we change the particle size distribution) at constant packing fraction and at constant pressure, and isotropic compression. For each deformation, we show that there are two classes of changes in the interparticle contact networks: jump changes and point changes. Jump changes occur when a contact network becomes mechanically unstable, particles "rearrange", and the potential energy (when the strain is applied at constant packing fraction) or enthalpy (when the strain is applied at constant pressure) and all derivatives are discontinuous. During point changes, a single contact is either added to or removed from the contact network. For repulsive linear spring interactions, second- and higher-order derivatives of the potential energy/enthalpy are discontinuous at a point change, while for Hertzian interactions, third- and higher-order derivatives of the potential energy/enthalpy are discontinuous. We illustrate the importance of point changes by studying the transition from a hexagonal crystal to a disordered crystal induced by applying polydispersity strain. During this transition, the system only undergoes point changes, with no jump changes. We emphasize that one must understand point changes, as well as jump changes, to predict the mechanical properties of jammed packings.

We present contactless atomic-force microscopy measurements of the hydrodynamic interactions between a rigid sphere and an air bubble in water at the micro-scale. The size of the bubble is found to have a significant effect on the response due to the long-range capillary deformation of the air-water interface. To rationalize the experimental data, we develop a viscocapillary lubrication model accounting for the finite-size effect. The comparison between experiments and theory allows us to measure the air-water surface tension, without contact, paving the way towards robust contactless tensiometry of polluted air-water interfaces.

Colloidal assembly at fluid interfaces has a great potential for the bottom-up fabrication of novel structured materials. However, challenges remain in realizing controllable and tunable assembly of particles into diverse structures. Herein, we report the capillary assembly of magnetic ellipsoidal Janus particles at a fluid-fluid interface. Depending on their tilt angle, i.e. the angle the particle main axis forms with the fluid interface, these particles deform the interface and generate capillary dipoles or hexapoles. Driven by capillary interactions, multiple particles thus assemble into chain-, hexagonal lattice- and ring-like structures, which can be actively controlled by applying an external magnetic field. We predict a field-strength phase diagram in which various structures are present as stable states. Owing to the diversity, controllability, and tunability of assembled structures, magnetic ellipsoidal Janus particles at fluid interfaces could therefore serve as versatile building blocks for novel materials.

We investigate how light polarization affects the motion of photo-responsive algae, \textit{Euglena gracilis}. In a uniformly polarized field, cells swim approximately perpendicular to the polarization direction and form a nematic state with zero mean velocity. When light polarization varies spatially, cell motion is modulated by local polarization. In such light fields, cells exhibit complex spatial distribution and motion patterns which are controlled by topological properties of the underlying fields; we further show that ordered cell swimming can generate directed transporting fluid flow. Experimental results are quantitatively reproduced by an active Brownian particle model in which particle motion direction is nematically coupled to local light polarization.

In a recent work [\textit{J. Mol. Liq}, 2020, \textbf{320}, 114420], using molecular dynamics simulations and a core-softened potential approach, we have shown that adding a simple solute as methanol can "kill" the density anomalous behavior as the LLCP is suppressed by the spontaneous crystallization in a hexagonal closed packing (HCP) crystal near the LLPT. Now, we extend this work in order to realize how longer-chain alcohols will affect the complex behavior of water-alcohol mixtures in the supercooled regime. Besides core-softened (CS) methanol, ethanol and 1-propanol were added to a system of identical particles that interact through the continuous shouldered well (CSW) potential. We observed that the density anomaly gradually decreases its extension in phase diagrams until disappearing with the growth of the non-polar chain and the alcohol concentration, differently from the liquid-liquid phase transition (and the LLCP), which remained present in all analyzed mixtures, in according to \textit{Nature}, 2001, \textbf{409}, 692. For our model, the longer non-polar chains and higher concentrations gradually impact the competition between the scales in the CS potential, leading to a gradual disappearing of the anomalies until the TMD total disappearance is observed when the first coordination shell structure is also affected: the short-range ordering is favored, leading to less competition between short- and long-range ordering and, consequently, to the extinction of anomalies. Also, the non-polar chain size and concentration have an effect on the solid phases, favoring the hexagonal closed packed (HCP) solid and the amorphous solid phase over the body-centered cubic (BCC) crystal.