Colloidal adsorption in planar polymeric brushes.

The design of nano-functionalised membranes or channels, able to effectively adsorb pollutants in aqueous solutions, is a topic that is gaining a great deal of attention in the materials science community. With this work we explore, through a combination of scaling theories and molecular dynamics simulations, the adsorption of spherical non-deformable colloidal nanoparticles within planar polymeric brushes. Our strategy is twofold: first, we generalise the Alexander-de Gennes theory for planar homopolymeric brushes to the case of diblock copolymer brushes, then we map the adsorbing homopolymeric brushes onto a diblock copolymer system, where the adsorbed colloids and all interacting monomers are considered monomers in bad solvent and we apply the generalised scaling theory to this effective diblock copolymer. This allows the prediction of the average conformation of the grafted substrate, i.e. its average height, as a function of the amount of loaded particles, as well as the introduction of a continuous mapping between a homopolymeric brush, the fraction of loaded particles and the average height of the adsorbing substrate.

Conformation and dynamics of partially active linear polymers.

We perform numerical simulations of isolated, partially active polymers, driven out-of-equilibrium by a fraction of their monomers. We show that, if the active beads are all gathered in a contiguous block, the position of the section along the chain determines the conformational and dynamical properties of the system. Notably, one can modulate the diffusion coefficient of the polymer from active-like to passive-like just by changing the position of the active block. Further, we show that a slight modification of the self-propulsion rule may give rise to an enhancement of diffusion under certain conditions, despite a decrease of the overall polymer activity. Our findings may help in the modelisation of active biophysical systems, such as filamentous bacteria or worms.

Self-Organized States from Solutions of Active Ring Polymers in Bulk and under Confinement.

In the present work, we study, by means of numerical simulations, the structural and dynamical behavior of a suspension of active ring polymers in bulk and under lateral confinement. At high activity, when changing the distance between the confining planes and the polymers' density, we identify the emergence of a self-organized dynamical state, characterized by the coexistence of slowly diffusing clusters of rotating disks and faster rings moving in between them. We further assess that self-organization is robust in a range of polymer sizes, and we identify a critical value of the activity, necessary to trigger cluster formation. This system has distinctive features resembling at the same time polymers, liquid crystals, and active systems, where the interplay between activity, topology, and confinement leads to a spontaneous segregation in an initially one-component solution.

Nonmonotonous Translocation Time of Polymers across Pores.

Polymers confined in corrugated channels, i.e., channels of varying amplitude, display multiple local maxima and minima of the diffusion coefficient upon increasing their degree of polymerization N. We propose a theoretical effective free energy for linear polymers based on a Fick-Jacobs approach. We validate the predictions against numerical data, obtaining quantitative agreement for the effective free energy, the diffusion coefficient, and the mean first passage time. Finally, we employ the effective free energy to compute the polymer lengths N_{min} at which the diffusion coefficient presents a minimum: we find a scaling expression that we rationalize with a blob model. Our results could be useful to design porous adsorbers, that separate polymers of different sizes without the action of an external flow.

Activity-Induced Collapse and Arrest of Active Polymer Rings.

We investigate, using numerical simulations, the conformations of isolated active ring polymers. We find that their behavior depends crucially on their size: Short rings (N≲100) swell, whereas longer rings (N≳200) collapse, at sufficiently high activity. By investigating the nonequilibrium process leading to the steady state, we find a universal route driving both outcomes; we highlight the central role of steric interactions, at variance with linear chains, and of topology conservation. We further show that the collapsed rings are arrested by looking at different observables, all underlining the presence of an extremely long timescales at the steady state, associated with the internal dynamics of the collapsed section. Finally, we found that in some circumstances the collapsed state spins about its axis.

Shape control of soft patchy nanoparticles under confinement.

Molecular building blocks undergoing a hierarchical assembly process form nano-scale objects which can further assemble into supramolecular structures. When the intermediate units have a limited valence in bonding, complex structures with tailored properties can be created. Here, we consider a composite, star-shaped particle made of f diblock copolymer chains uniformly grafted on a spherical colloid and investigate its first self-assembly stage both in the bulk and under lateral confinement. By means of numerical simulations, we show that, in the bulk, this system develops aggregates whose number and size depend on the temperature as well as on the relative ratio of solvophobic monomers. The emerging aggregates are referred to as patches and impart directionality in bonding to the complex particle. We further characterize how we can control, by changing the lateral confinement, the shape of the brush and the patch properties as a function of the distance between the confining walls. We find that the number of the patches can be determined by tuning the degree of confinement imposed on the particle. Finally, we employ a continuum mechanics model, known as the Liquid Drop Model, to gain insight into the elastic properties of the system. This theoretical approach allows to connect the patch properties to the elastic response of the composite particle.

Designer protein assemblies with tunable phase diagrams in living cells.

Protein self-organization is a hallmark of biological systems. Although the physicochemical principles governing protein-protein interactions have long been known, the principles by which such nanoscale interactions generate diverse phenotypes of mesoscale assemblies, including phase-separated compartments, remain challenging to characterize. To illuminate such principles, we create a system of two proteins designed to interact and form mesh-like assemblies. We devise a new strategy to map high-resolution phase diagrams in living cells, which provide self-assembly signatures of this system. The structural modularity of the two protein components allows straightforward modification of their molecular properties, enabling us to characterize how interaction affinity impacts the phase diagram and material state of the assemblies in vivo. The phase diagrams and their dependence on interaction affinity were captured by theory and simulations, including out-of-equilibrium effects seen in growing cells. Finally, we find that cotranslational protein binding suffices to recruit a messenger RNA to the designed micron-scale structures.

Globulelike Conformation and Enhanced Diffusion of Active Polymers.

We study the dynamics and conformation of polymers composed by active monomers. By means of Brownian dynamics simulations we show that, when the direction of the self-propulsion of each monomer is aligned with the backbone, the polymer undergoes a coil-to-globulelike transition, highlighted by a marked change of the scaling exponent of the gyration radius. Concurrently, the diffusion coefficient of the center of mass of the polymer becomes essentially independent of the polymer size for sufficiently long polymers or large magnitudes of the self-propulsion. These effects are reduced when the self-propulsion of the monomers is not bound to be tangent to the backbone of the polymer. Our results, rationalized by a minimal stochastic model, open new routes for activity-controlled polymers and, possibly, for a new generation of polymer-based drug carriers.

Tuning the order of colloidal monolayers: assembly of heterogeneously charged colloids close to a patterned substrate.

We study the behavior of negatively charged colloids with two positively charged polar caps close to a planar patterned surface. The competition between the different anisotropic components of the particle-particle interaction is able by itself to give rise to a rich assembly scenario: colloids with charged surface patterns already form different crystalline domains when adsorbed to a homogeneously charged substrate. Here we consider substrates composed of alternating (negative/neutral, positive/neutral and positive/negative) parallel stripes and, by means of Monte Carlo simulations, we investigate the ordering of the colloids on changing the number of the stripes. We show that the additional competition between the two different lengths scales characterizing the system (i.e., the particle interaction range and the size of the stripes) gives rise to a plethora of distinct particle arrangements, where some well-defined trends can be observed. By accurately tuning the substrate charged motif it is possible to, e.g., promote specific particle arrangements, disfavor crystalline domains or induce the formation of extended, open clusters.

An Accurate Estimate of the Free Energy and Phase Diagram of All-DNA Bulk Fluids.

We present a numerical study in which large-scale bulk simulations of self-assembled DNA constructs have been carried out with a realistic coarse-grained model. The investigation aims at obtaining a precise, albeit numerically demanding, estimate of the free energy for such systems. We then, in turn, use these accurate results to validate a recently proposed theoretical approach that builds on a liquid-state theory, the Wertheim theory, to compute the phase diagram of all-DNA fluids. This hybrid theoretical/numerical approach, based on the lowest-order virial expansion and on a nearest-neighbor DNA model, can provide, in an undemanding way, a parameter-free thermodynamic description of DNA associating fluids that is in semi-quantitative agreement with experiments. We show that the predictions of the scheme are as accurate as those obtained with more sophisticated methods. We also demonstrate the flexibility of the approach by incorporating non-trivial additional contributions that go beyond the nearest-neighbor model to compute the DNA hybridization free energy.

Condensation and Demixing in Solutions of DNA Nanostars and Their Mixtures.

We present a numerical/theoretical approach to efficiently evaluate the phase diagram of self-assembling DNA nanostars. Combining input information based on a realistic coarse-grained DNA potential with the Wertheim association theory, we derive a parameter-free thermodynamic description of these systems. We apply this method to investigate the phase behavior of single components and mixtures of DNA nanostars with different numbers of sticky arms, elucidating the role of the system functionality and of salt concentration. Specifically, we evaluate the propensity to demix, the gas-liquid phase boundaries and the location of the critical points. The predicted critical parameters compare very well with existing experimental results for the available compositions. The approach developed here is very general, easily extensible to other all-DNA systems, and provides guidance for future experiments.

Multiblob coarse-graining for mixtures of long polymers and soft colloids.

Soft nanocomposites represent both a theoretical and an experimental challenge due to the high number of the microscopic constituents that strongly influence the behaviour of the systems. An effective theoretical description of such systems invokes a reduction of the degrees of freedom to be analysed, hence requiring the introduction of an efficient, quantitative, coarse-grained description. We here report on a novel coarse graining approach based on a set of transferable potentials that quantitatively reproduces properties of mixtures of linear and star-shaped homopolymeric nanocomposites. By renormalizing groups of monomers into a single effective potential between a f-functional star polymer and an homopolymer of length N0, and through a scaling argument, it will be shown how a substantial reduction of the to degrees of freedom allows for a full quantitative description of the system. Our methodology is tested upon full monomer simulations for systems of different molecular weight, proving its full predictive potential.

Single-File Escape of Colloidal Particles from Microfluidic Channels.

Single-file diffusion is a ubiquitous physical process exploited by living and synthetic systems to exchange molecules with their environment. It is paramount to quantify the escape time needed for single files of particles to exit from constraining synthetic channels and biological pores. This quantity depends on complex cooperative effects, whose predominance can only be established through a strict comparison between theory and experiments. By using colloidal particles, optical manipulation, microfluidics, digital microscopy, and theoretical analysis we uncover the self-similar character of the escape process and provide closed-formula evaluations of the escape time. We find that the escape time scales inversely with the diffusion coefficient of the last particle to leave the channel. Importantly, we find that at the investigated microscale, bias forces as tiny as 10^{-15} N determine the magnitude of the escape time by drastically reducing interparticle collisions. Our findings provide crucial guidelines to optimize the design of micro- and nanodevices for a variety of applications including drug delivery, particle filtering, and transport in geometrical constrictions.

Active Brownian particles escaping a channel in single file.

Active particles may happen to be confined in channels so narrow that they cannot overtake each other (single-file conditions). This interesting situation reveals nontrivial physical features as a consequence of the strong interparticle correlations developed in collective rearrangements. We consider a minimal two-dimensional model for active Brownian particles with the aim of studying the modifications introduced by activity with respect to the classical (passive) single-file picture. Depending on whether their motion is dominated by translational or rotational diffusion, we find that active Brownian particles in single file may arrange into clusters that are continuously merging and splitting (active clusters) or merely reproduce passive-motion paradigms, respectively. We show that activity conveys to self-propelled particles a strategic advantage for trespassing narrow channels against external biases (e.g., the gravitational field).

Morphological transitions of droplets wetting rectangular domains.

We report the results of comprehensive experiments and numerical calculations of interfacial morphologies of water confined to the hydrophilic top face of rectangular posts of width W = 500 µm and lengths between L = 5W and 30W. A continuous evolution of the interfacial shape from a homogeneous liquid filament to a bulged filament and back is observed during changes in the liquid volume. Above a certain threshold length of L* = 16.0W, the transition between the two morphologies is discontinuous and a bistability of interfacial shapes is observed in a certain interval of the reduced liquid volume V/W(3).