No Arabic abstract
Spontaneous self-assembly in molecular systems is a fundamental route to both biological and engineered soft matter. Simple micellisation, emulsion formation, and polymer mixing principles are well understood. However, the principles behind emergence of structures with competing length scales in soft matter systems remain an open question. Examples include the droplet-inside-droplet assembly in many biomacromolecular systems undergoing liquid-liquid phase separation, analogous multiple emulsion formation in oil-surfactant-water formulations, and polymer core-shell particles with internal structure. We develop here a microscopic theoretical model based on effective interactions between the constituents of a soft matter system to explain self-organization both at single and multiple length scales. The model identifies how spatial ordering at multiple length scales emerges due to competing interactions between the system components, e.g. molecules of different sizes and different chemical properties. As an example of single and multiple-length-scale assembly, we map out a generic phase diagram for a solution with two solute species differing in their mutual and solvent interactions. By performing molecular simulations on a block-copolymer system, we further demonstrate how the phase diagram can be connected to a molecular system that has a transition from regular single-core polymer particles to multi-core aggregates that exhibit multiple structural length scales. The findings provide guidelines to understanding the length scales rising spontaneously in biological self-assembly, but also open new venues to the development and engineering of biomolecular and polymeric functional materials.
A rigid cylinder placed on a soft gel deforms its surface. When multiple cylinders are placed on the surface, they interact with each other via the topography of the deformed gel which serves as an energy landscape; as they move, the landscape changes which in turn changes their interaction. We use a combination of experiments, simple scaling estimates and numerical simulations to study the self-assembly of cylinders in this elastic analog of the Cheerios effect for capillary interactions on a fluid interface. Our results show that the effective two body interaction can be well described by an exponential attraction potential as a result of which the dynamics also show an exponential behavior with respect to the separation distance. When many cylinders are placed on the gel, the cylinders cluster together if they are not too far apart; otherwise their motion gets elastically arrested.
Using small-angle neutron scattering, we demonstrate that the complex magnetic domain patterns at the surface of Nd2Fe14B, revealed by quantitative Kerr and Faraday microscopy, propagate into the bulk and exhibit structural features with dimensions down to 6 nm, the domain wall thickness. The observed fractal nature of the domain structures provides an explanation for the anomalous increase in the bulk magnetization of Nd2Fe14B below the spin-reorientation transition. These measurements open up a rich playground for studies of fractal structures in highly anisotropic magnetic systems.
Recent progress in the understanding of the effect of electrostatics in soft matter is presented. A vast amount of materials contains ions ranging from the molecular scale (e.g., electrolyte) to the meso/macroscopic one (e.g., charged colloidal particles or polyelectrolytes). Their (micro)structure and physicochemical properties are especially dictated by the famous and redoubtable long-ranged Coulomb interaction. In particular theoretical and simulational aspects, including the experimental motivations, will be discussed.
Nanoparticles in solution acquire charge through dissociation or association of surface groups. Thus, a proper description of their electrostatic interactions requires the use of charge-regulating boundary conditions rather than the commonly employed constant-charge approximation. We implement a hybrid Monte Carlo/Molecular Dynamics scheme that dynamically adjusts the charges of individual surface groups of objects while evolving their trajectories. Charge-regulation effects are shown to qualitatively change self-assembled structures due to global charge redistribution, stabilizing asymmetric constructs. We delineate under which conditions the conventional constant-charge approximation may be employed and clarify the interplay between charge regulation and dielectric polarization.
Chiral heteropolymers such as larger globular proteins can simultaneously support multiple length scales. The interplay between different scales brings about conformational diversity, and governs the structure of the energy landscape. Multiple scales produces also complex dynamics, which in the case of proteins sustains live matter. However, thus far no clear understanding exist, how to distinguish the various scales that determine the structure and dynamics of a complex protein. Here we propose a systematic method to identify the scales in chiral heteropolymers such as a protein. For this we introduce a novel order parameter, that not only reveals the scales but also probes the phase structure. In particular, we argue that a chiral heteropolymer can simultaneously display traits of several different phases, contingent on the length scale at which it is scrutinized. Our approach builds on a variant of Kadanoffs block-spin transformation that we employ to coarse grain piecewise linear chains such as the C$alpha$ backbone of a protein. We derive analytically and then verify numerically a number of properties that the order parameter can display. We demonstrate how, in the case of crystallographic protein structures in Protein Data Bank, the order parameter reveals the presence of different length scales, and we propose that a relation must exist between the scales, phases, and the complexity of folding pathways.