Simulation of Vertical Surfactant Distributions in Drying Latex Films.

Following our previous contribution ( Gromer, A. et al. Langmuir 2015 , 31 , 10983 - 10994 ) presenting a new simulation tool devoted to particle distributions in drying latex films, this Article describes the prediction of surfactant concentration profiles in the vertical direction during the complete film formation process. The simulation is inspired by cellular automata and equations by Routh and co-workers. It includes effects that were not considered before: surfactant convection by water and surfactant desorption upon particle deformation. It is based on five parameters describing the nature of the polymer/surfactant system and on film formation conditions. In particular, the viscoelastic properties of the polymer were taken into account through the λ̅ parameter introduced by Routh and Russel. Results show the importance of convection by water and the influence of the particular deformation mechanism on the final surfactant distribution. Excesses or depletions can be predicted either on the surface or on the substrate sides, in qualitative agreement with the numerous existing experimental studies. The complex interplay between parameters governing surfactant distributions makes the results unpredictable without the help of such a simulation tool. Therefore, it should be of interest to both industrial and academic scientists.

Horizontal drying fronts in films of colloidal dispersions: influence of hydrostatic pressure and collective diffusion.

The origin and time evolution of heterogeneities in drying colloidal films is still a matter of debate. In this work, we studied the behaviour of horizontal drying fronts in a 1D configuration. The effects of hydrostatic pressure and collective diffusion of charged particles, neglected so far, were introduced. We made use of the new simulation tool based on cellular automata we recently presented (Langmuir 2015 & 2017). To check the simulation results, measurements of film profiles in the wet state and drying front velocities were performed with silica colloids. It was shown that taking hydrostatic pressure into account much improves agreement between theory and experiment. On the other hand, the simulation showed that collective diffusion slows down the drying fronts, even more when the Debye length is increased. This latter effect remains to be checked experimentally. This work opens the way to further improvements of theory and simulation, notably 2D and 3D simulations.

Simulation of Latex Film Formation Using a Cell Model in Real Space: Vertical Drying.

This paper presents a simulation tool applied to latex film formation by drying, a hybrid between a classical numerical resolution method using finite differences and cellular automata, and making use of object-oriented programming. It consists of dividing real space into cells and applying local physical laws to simulate the exchange of matter between neighboring cells. In a first step, the simulation was applied to the simple case of vertical drying of a latex containing only one population of monodisperse particles and water. Our results show how the distribution of latex particles evolves through the different drying stages due to a combination of diffusion, convection, and particle deformation. While repulsive interactions between the particles tend to favor homogeneous distributions in the first drying stage, concentration gradients that develop in opposite ways can be observed depending on the drying regime. The distributions, calculated in various cases, reproduce and extend several theoretical results and are in qualitative agreement with some experimental findings.

Thermodynamic approach to phase coexistence in ternary phospholipid-cholesterol mixtures.

We introduce a simple and predictive model for determining the phase stability of ternary phospholipid-cholesterol mixtures. Assuming that competition between the liquid and gel order of the phospholipids is the main driving force behind lipid segregation, we derive a Gibbs free energy of mixing, based on the thermodynamic properties of the lipids main transition. A numerical approach was devised that enables the fast and efficient determination of the ternary diagrams associated with our Gibbs free energy. The computed phase coexistence diagram of DOPC/DPPC/cholesterol reproduces well-known features for this system at 10 °C, as well as its evolution with temperature.

A schematic model for molecular affinity and binding with Ising variables.

After discussing the relevance of statistical physics in molecular recognition processes, we present a schematic model for ligand-receptor association based on an Ising chain. We discuss the possible behaviors of the affinity when the stiffness of the ligand increases. We also consider the case of flexible receptors. A variety of interesting behaviors is obtained, including some affinity modulation upon bond hardening or softening. The affinity of a ligand for its receptor is shown to depend on the details of its rigidity profile, and we question the possibility of encoding information in the rigidities as well as in the shape. An exhaustive study of the selectivity of patterns with length n < 8 is carried out. Connection with other spin models, in particular spin glasses is mentioned in the conclusion.

Velocity of lateral drying fronts in film formation by drying of colloidal dispersions. A 2D simulation.

Drying of colloids is always heterogeneous and proceeds by progression of drying fronts in various directions at various velocities. The fundamental mechanisms at the origin of appearance and motion of drying fronts are still not totally understood. This article addresses these questions in the case of lateral drying fronts by using the new simulation tool based on cellular automata we recently developed (Langmuir 2015 and 2017). For the first time, a 2D simulation is proposed. Silica dispersions were used as model colloids to test the simulation. Film profiles were measured during drying by optical profilometry as well as front velocities by image processing. In the cases of non-circular deposits (squares and rectangles), drying fronts in the plane of the film (x,y plane, x being the longest side in the case of a rectangle) do not move at the same speed along sides and diagonals, the velocity order being diagonal >x (longest side) >y (shortest side). The velocity contrast (difference between x and y sides) increases with the aspect ratio of the rectangle. This behavior is explained and accounted for by the 2D simulation presented in this article. Experimental results reasonably well validate the simulation.

Lipid bilayer adhesion on sparse DNA carpets: theoretical analysis of membrane deformations induced by single-end-grafted polymers.

We consider a single-end-grafted polymer chain covered by a membrane in contact with a flat and rigid surface in the context of supported membrane adhesion on surfaces carrying dilute polymer brushes. The fluid membrane adheres to the surface due to attractive interactions; the presence of a macromolecule locally hinders the membrane-surface contact and creates a protuberant membrane bulge. We study both the size and elevation of such membrane deformations as a function of curvature modulus, surface tension, adhesion energy, and chain size. Scaling results are derived, valid for both ideal and nonideal chain statistics, leading to complex diagrams of states depending on curvature modulus, tension, and adhesion values. We also compute quantitatively the membrane deformation profile for shallow bulges and make predictions for realistic systems involving DNA grafted chains covered by lipid membranes.

Enhanced shear separation for chiral magnetic colloidal aggregates.

We study the designing principles of the simplest colloidal propeller, an architecture built from four identical spheres that can couple translation with rotation to produce controlled drift motion. By considering superparamagnetic beads, we show that the simultaneous action of a magnetic field and a shear flow leads to the migration of the cluster in the vorticity direction. We investigate the dependence of the migration velocity on the geometrical parameters of the cluster and find that significant cluster separation can be achieved under the typical operation conditions of microfluidic devices.

Measuring the kinetics of biomolecular recognition with magnetic colloids.

We introduce a general methodology based on magnetic colloids to study the recognition kinetics of tethered biomolecules. Access to the full kinetics of the reaction is provided by an explicit measure of the time evolution of the reactant densities. Binding between a single ligand and its complementary receptor is here limited by the colloidal rotational diffusion. It occurs within a binding distance that can be extracted by a reaction-diffusion theory that properly accounts for the rotational Brownian dynamics. Our reaction geometry allows us to probe a large diversity of bioadhesive molecules and tethers, thus providing a quantitative guidance for designing more efficient reactive biomimetic surfaces, as required for diagnostic, therapeutic, and tissue engineering techniques.

What is in a pebble shape?

We propose to characterize the shapes of flat pebbles in terms of the statistical distribution of curvatures measured along the pebble contour. This is demonstrated for the erosion of clay pebbles in a controlled laboratory apparatus. Photographs at various stages of erosion are analyzed, and compared with two models. We find that the curvature distribution complements the usual measurement of aspect ratio, and connects naturally to erosion processes that are typically faster at protruding regions of high curvature.

Prediction and statistics of pseudoknots in RNA structures using exactly clustered stochastic simulations.

Ab initio RNA secondary structure predictions have long dismissed helices interior to loops, so-called pseudoknots, despite their structural importance. Here we report that many pseudoknots can be predicted through long-time-scale RNA-folding simulations, which follow the stochastic closing and opening of individual RNA helices. The numerical efficacy of these stochastic simulations relies on an O(n2) clustering algorithm that computes time averages over a continuously updated set of n reference structures. Applying this exact stochastic clustering approach, we typically obtain a 5- to 100-fold simulation speed-up for RNA sequences up to 400 bases, while the effective acceleration can be as high as 105-fold for short, multistable molecules (