Soft Matter最新文献

pH responsive self-assembled supramolecular systems in water hold tremendous promise spanning across the various realms of science and technology. Herein, we report the design and synthesis of benzyl viologen (BV) based amphiphiles and their ability to form pH responsive aggregates with a water soluble anionic dye (electron donor), a polyelectrolyte (PE), and a surfactant. To counter the low solubility of viologen derivatives, β-cyclodextrin (β-CD) was employed as a solubility promoter and the host-guest complexes were characterized by NMR spectroscopy. The impacts of increasing the number of benzyl units on (i) the water solubility of viologens, (ii) the response of the aggregates of viologens with pyranine, PE, and surfactants towards pH, and (iii) the influence of β-CD on the pH-responsive nature of BV-pyranine, BV-PE, BV-surfactant, etc. were investigated. Apart from improving the solubility of viologens, β-CD also imparted pH-responsive dissolution/aggregation behavior to the viologen-anionic polyelectrolyte and viologen-anionic surfactant complexes. The pH switchable behaviour of the soft supramolecular aggregates in water was rationalized in light of a delicate balance prevailing between multiple non-covalent interactions. Based on the results, we propose an elegant molecular design principle to generate pH responsive colloidal aggregates from amphiphiles and oppositely charged molecular systems.

We measure the dynamical behavior of colloidal singlets and dumbbells on an inclined magnetic moiré pattern, subject to a precessing external homogeneous magnetic field. At low external field strength single colloidal particles and dumbbells move everywhere on the pattern: at stronger external field strengths colloidal singlets and dumbbells are localized in generic locations. There are however nongeneric locations of flat channels that cross the moiré Wigner Seitz cell. In the flat channels we find gravitational driven translational and non-translational dynamic phase behavior of the colloidal singlets and dumbbells depending on the external field strength and the precession angle of the external homogeneous magnetic field.

The phase behavior of symmetric diblock copolymers under three-dimensional (3D) soft confinement is investigated using self-consistent field theory. Soft confinement is realized in binary blends composed of AB diblock copolymers and C homopolymers, where the copolymers self-assemble to form a droplet embedded in a homopolymer matrix. The phase behavior of the confined block copolymers is regulated by the degree of confinement and the selectivity of the homopolymers, resulting in a rich variety of novel structures. When the C homopolymers are neutral to the A- and B-blocks, stacked lamellae (SL) are formed where the number of layers increases with the droplet volume, resulting in a morphological transition sequence from Janus particles to square SL. When the C homopolymers are strongly selective for the B-blocks, a series of non-lamellar morphologies, including onion-, hamburger-, cross-, ring-, and cookie-like structures, are observed. A detailed free energy analysis reveals a first-order reversible transformation between SL and onion-like (OL) structures when the selectivity of the homopolymers is changed. Our results provide a comprehensive understanding of how various factors, such as the copolymer concentration, homopolymer chain length, degree of confinement, and homopolymer selectivity, affect the self-assembled structures of diblock copolymers under soft 3D confinement.

Control of individual micromotors within a group would allow for improved efficiency, greater ability to accomplish complex tasks, higher throughput, and increased adaptability. However, independent control of micromotors remains a significant challenge. Typical actuation techniques, such as chemical and magnetic, are uniform over the workspace and therefore cannot control one micromotor independently of the others. To address this challenge, we demonstrate a novel control method of applying a localized region of UV light that activates a single light-responsive TiO₂ micromotor at a time. To achieve this, a digital micromirror device (DMD) was employed which is capable of highly precise localized illumination. To demonstrate this precise user-defined control, patterns of micromotors were created via selective actuation and magnetic steering. In addition, a closed-loop system was also developed which automates the guidance of individual micromotors to specified locations, illustrating the potential for more efficient and precise control of the micromotors.

The self-organisation of individual suspended colloids into ordered structures that can be mediated by confinement has garnered interest recently. Despite the push for solvent reduction for sustainability reasons, the comprehension and development of solvent-free assembly methods remain largely unaddressed. In this study, we explore the effect of confinement without rigid geometrical constraints, i.e., wall-less confinement on the assembly of monodisperse PMMA powder microspheres (diameters of 3 μm and 10 μm) on fluorocarbon-patterned heterogeneous substrates using a solvent-free rubbing assembly approach. Our findings reveal that the PMMA microspheres self-align on the fluorocarbon patterns, adapting to various geometrical shapes of these patterns through symmetry matching. The assembly process is driven by triboelectric charging and elastic properties of the microspheres and substrates. Moreover, we observe that the host substrate and the particle and pattern size ratio significantly influence the ordering of the microparticles on the fluorocarbon patterns. Ultimately, we demonstrate the successful use of fluorocarbon patterns to assemble tunable crystal patterns on rigid substrates, which typically do not exhibit any ordering.

Trilayer electrochemical actuators comprising an electrolyte layer sandwiched between two electrode layers have been shown to exhibit large deformations at low actuation voltages. Here we report the aerosol-jet printing (AJP) of high-aspect-ratio bending-type trilayer electrochemical microactuators comprised of Nafion as the electrolyte and poly(3,4-ethylenedioxythiophene)polystyrene sulfonate (PEDOT:PSS) as the electrode. We investigated how the thicknesses of the electrolyte and electrode layers affect the DC response of these actuators by fabricating high-aspect-ratio trilayer cantilevers with varied layer thicknesses (0.36 μm to 1.9 μm-thick electrodes, and 3.5 μm to 12 μm-thick electrolyte layers). We found that the transported charge and angular deflection are proportional to the applied voltage at steady state, and the charge-to-voltage ratio scales with the PEDOT:PSS thickness. The deflection-to-voltage ratio is found to be strongly affected by the Nafion electrolyte thickness, showing a decreasing trend, but is less affected by the PEDOT:PSS thickness in the range of dimensions fabricated. The timescales for deflection are found to be generally longer than the timescales for charge transfer and no clear trend is observed with respect to layer thicknesses. This work establishes an experimental protocol in geometry optimisation of printed electrochemical microactuators, verifies the applicability of a theoretical model, and lays the groundwork for designing and optimising more sophisticated printed electrochemical microactuation systems.

Most passive droplet transport strategies rely on spatial variations of material properties to drive droplet motion, leading to gradient-based mechanisms with intrinsic length scales that limit the droplet velocity or the transport distance. Here, we propose droplet fibrotaxis, a novel mechanism that leverages an anisotropic fiber-reinforced deformable solid to achieve spontaneous and gradient-free droplet transport. Using high-fidelity simulations, we identify the fluid wettability, fiber orientation, anisotropy strength and elastocapillary number as critical parameters that enable controllable droplet velocity and long-range droplet transport. Our results highlight the potential of fibrotaxis as a droplet transport mechanism that can have a strong impact on self-cleaning surfaces, water harvesting and medical diagnostics.

Collagenolytic degradation is a process fundamental to tissue remodeling. The microarchitecture of collagen fibril networks changes during development, aging, and disease. Such changes to microarchitecture are often accompanied by changes in matrix degradability. In a matrix, the pore size and fibril characteristics such as length, diameter, number, orientation, and curvature are the major variables that define the microarchitecture. In vitro, collagen matrices of the same concentration but different microarchitectures also vary in degradation rate. How do different microarchitectures affect matrix degradation? To answer this question, we developed a computational model of collagen degradation. We first developed a lattice model that describes collagen degradation at the scale of a single fibril. We then extended this model to investigate the role of microarchitecture using Brownian dynamics simulation of enzymes in a multi-fibril three dimensional matrix to predict its degradability. Our simulations predict that the distribution of enzymes around the fibrils is non-uniform and depends on the microarchitecture of the matrix. This non-uniformity in enzyme distribution can lead to different extents of degradability for matrices of different microarchitectures. Our simulations predict that for the same enzyme concentration and collagen concentration, a matrix with thicker fibrils degrades more than that with thinner fibrils. Our model predictions were tested using in vitro experiments with synthetic collagen gels of different microarchitectures. Experiments showed that indeed degradation of collagen depends on the matrix architecture and fibril thickness. In summary, our study shows that the microarchitecture of the collagen matrix is an important determinant of its degradability.

Systems switching between different dynamical phases is a ubiquitous phenomenon. The general understanding of such a process is limited. To this end, we present a general expression that captures fluctuations of a system exhibiting a switching mechanism. Specifically, we obtain an exact expression of the Laplace-transformed characteristic function of the particle's position. Then, the characteristic function is used to compute the effective diffusion coefficient of a system performing intermittent dynamics. Furthermore, we employ two examples: (1) generalized run-and-tumble active particle, and (2) an active particle switching its dynamics between generalized active run-and-tumble motion and passive Brownian motion. In each case, explicit computations of the spatial cumulants are presented. Our findings reveal that the particle's position probability density function exhibit rich behaviours due to intermittent activity. Numerical simulations confirm our findings.

We study the influence of airborne CO₂ on the charge state of carboxylate stabilized polymer latex particles suspended in aqueous electrolytes. We combine conductometric experiments interpreted in terms of Hessinger's conductivity model with Poisson-Boltzmann cell (PBC) model calculations with charge regulation boundary conditions. Without CO₂, a minority of the weakly acidic surface groups are dissociated and only a fraction of the total number of counter-ions actually contribute to conductivity. The remaining counter-ions exchange freely with added other ions like Na⁺, K⁺ or Cs⁺. From the PBC-calculations we infer a corresponding pK_a of 4.26 as well as a renormalized charge in reasonably good agreement with the number of freely mobile counter-ions. Equilibration of salt- and CO₂-free suspensions against ambient air leads to a drastic de-charging, which exceeds by far the expected effects of to dissolved CO₂ and its dissociation products. Further, no counter-ion-exchange is observed. To reproduce the experimental findings, we have to assume an effective pK_a of 6.48. This direct influence of CO₂ on the state of surface group dissociation explains our recent finding of a CO₂-induced decrease of the ζ-potential and supports the suggestion of an additional charge regulation caused by molecular CO₂. Given the importance of charged surfaces in contact with aqueous electrolytes, we anticipate that our observations bear substantial theoretical challenges and important implications for applications ranging from desalination to bio-membranes.