Effect of polymer architecture on the adsorption behaviour of amphiphilic copolymers: A theoretical study.

Hypothesis: Polymer architecture is known to have significant impact on its adsorption behaviour. Most studies have been concerned with the more concentrated, "close to surface saturation" regime of the isotherm, where complications such as lateral interactions and crowding also additionally affect the adsorption. We compare a variety of amphiphilic polymer architectures by determining their Henry's adsorption constant (k), which, as with other surface active molecules, is the proportionality constant between surface coverage and bulk polymer concentration in a sufficiently dilute regime.

Hybrid Molecules Consisting of Lysine Dendrons with Several Hydrophobic Tails: A SCF Study of Self-Assembling.

In this article, we used the numerical self-consistent field method of Scheutjens-Fleer to study the micellization of hybrid molecules consisting of one polylysine dendron with charged end groups and several linear hydrophobic tails attached to its root. The main attention was paid to spherical micelles and the determination of the range of parameters at which they can appear. A relationship has been established between the size and internal structure of the resulting spherical micelles and the length and number of hydrophobic tails, as well as the number of dendron generations.

Colloidal particles interacting with a polymer brush: a self-consistent field theory.

The interaction of colloidal particles with a planar polymer brush immersed in a solvent of variable thermodynamic quality is studied by a numerical self-consistent field method combined with analytical mean-field theory. The effect of embedded particle on the distribution of polymer density in the brush is analyzed and the particle insertion free energy profiles are calculated for variable size and shape of the particles and sets of polymer-particle and polymer-solvent interaction parameters. In particular, both cases of repulsive and attractive interactions between particles and brush-forming chains are considered.

The physics of microemulsions extracted from modeling balanced tensionless surfactant-loaded liquid-liquid interfaces.

Microemulsions are explored using the self-consistent field approach. We consider a balanced model that features two solvents of similar size and a symmetric surfactant. Interaction parameter χ and surfactant concentration φ complement the model definition.

Computer modeling of polymer stars in variable solvent conditions: a comparison of MD simulations, self-consistent field (SCF) modeling and novel hybrid Monte Carlo SCF approach.

Computer-aided modeling is a systematic approach to grasp the physics of macromolecules, but it remains essential to know when to trust the results and when not. For a polymer star, we consider three approaches: (i) Molecular Dynamics (MD) simulations and implementing a coarse-grained model, (ii) the self-consistent field approach based on a mean-field approximation and implementing the lattice model due to Scheutjens and Fleer (SF-SCF) and (iii) novel hybrid Monte Carlo self-consistent field (MC-SCF) method, which combines a coarse-grained model driven by a Monte Carlo method and a mean-field representation driven by SF-SCF. We compare the performance of these approaches under a wide range of solvent qualities.

Bioflocculants from wastewater: Insights into adsorption affinity, flocculation mechanisms and mixed particle flocculation based on biopolymer size-fractionation.

Hypothesis: Microbial extracellular polymeric substances (EPS) produced from wastewater are generally heterodispersed, which is expected to influence their flocculation performances and mechanism, particularly in mixed particle systems. The different molecular weight (MW) fractions should contribute to the overall adsorption affinity and flocculation mechanism of EPS in single and dual clay systems.

Experiments: EPS harvested from bioreactors were size-fractionated into high, medium and low MW fractions (HMW, MMW, LMW, respectively).

Long Tails with Flower-like Conformations Undergo an Escape Transition in Homopolymer Adsorption Layers.

De Gennes predicted that homopolymer adsorption on a solid-liquid interface results in an adsorption profile with a proximal, a central, and a distal region, wherein, for a good solvent, the central region has a self-similar structure with a density profile that decays as a power law with a coefficient of -4/3. Recent numerical self-consistent field (SCF) predictions for the long-chain length () limit revealed a more complex central region with an inner part, where the loops dominate the layer, with a (mean-field) power-law coefficient of -2 and an outer part, where tails dominate, with a "de Gennes" scaling of -4/3. The tails with length < * contribute to the inner part of the central region, and these have similar conformations as the loops.

Turning autophobic wetting on biomimetic surfaces into complete wetting by wetting additives.

Autophobicity or pseudo partial wetting, a phenomenon of a liquid not spreading on its own monolayer, is characterized by an energy barrier that prevents the growth of a wetting film beyond the monolayer thickness. Applying a molecularly detailed self-consistent field theory we illustrate how autophobic wetting can be overcome by wetting additives. More specifically we use an emulsifier which keeps the interfacial tension between the wetting component and the majority solvent low, and a co-solvent additive which partitions inside the film and then destroys the molecular order in it so that the barrier for film growth is cleared.

Electroresponsive Polyelectrolyte Brushes Studied by Self-Consistent Field Theory.

End-grafting of polyelectrolyte chains to conducting substrates offers an opportunity to fabricate electro-responsive surfaces capable of changing their physical/chemical properties (adhesion, wettability) in response to applied electrical voltage. We use a self-consistent field numerical approach to compare the equilibrium properties of tethered strong and weak (pH-sensitive) polyelectrolytes to applied electrical field in both salt-free and salt-containing solutions. We demonstrate that both strong and weak polyelectrolyte brushes exhibit segregation of polyions in two populations if the surface is oppositely charged with respect to the brush.

Elastic properties of symmetric liquid-liquid interfaces.

The mean (κ) and Gaussian (κ[over ¯]) bending rigidities of liquid-liquid interfaces, of importance for shape fluctuations and topology of interfaces, respectively, are not yet established: Even their signs are debated. Using the Scheutjens Fleer variant of the self-consistent field theory, we implemented a model for a symmetric L-L interface and obtained high-precision (mean-field) results in the grand-canonical (μ,V,T) ensemble. We report positive values for both moduli when the system is close to critical where the rigidities show the same scaling behavior as the interfacial tension γ.

(Homo)polymer-mediated colloidal stability of micellar solutions.

Despite their wide range of applications, there is a remarkable lack of fundamental understanding about how micelles respond to other components in solution. The colloidal stability of micellar solutions in presence of (homo)polymers is investigated here following a theoretical bottom-up approach. A polymer-mediated micelle-micelle interaction is extracted from changes in the micelle-unimer equilibrium as a function of the inter-micelle distance.

Non-linear elasticity effects and stratification in brushes of branched polyelectrolytes.

Brushes formed by arm-tethered starlike polyelectrolytes may exhibit internal segregation into weakly and strongly extended populations (stratified two-layer structure) when strong ionic intermolecular repulsions induce stretching of the tethers up to the limit of their extensibility. We propose an approximate Poisson-Boltzmann theory for analysis of the structure of the stratified brush and compare it with results of numerical self-consistent field modeling. Both analytical and numerical models point to the formation of a narrow cloud of counterions (internal double electrical layer) localized inside a stratified brush at the boundary between the layers.

Plasticity in colloidal gel strands.

Colloidal gels are space-spanning networks of aggregated particles. The mechanical response of colloidal gels is governed, to a large extent, by the properties of the individual gel strands. To study how colloidal gels respond to repeated deformations, we perform Brownian dynamics simulations on single strands of aggregated colloidal particles.

Temperature-Induced Re-Entrant Morphological Transitions in Block-Copolymer Micelles.

Using a combination of a mean-field theoretical method and the numerical Scheutjens-Fleer self-consistent field approach, we predict that it is possible to have re-entrant morphological transitions in nanostructures of diblock copolymers upon variation in temperature-mediated solubility of the associating blocks. This peculiar effect is explained by the different rates in variation of the density of the collapsed core domains and the corresponding interfacial energy as a function of the temperature. The theoretical findings are supported by existing experimental observations of reversed sequences of the morphological transitions occurring upon temperature variation in solutions of amphiphilic block copolymers.

Structure and properties of polydisperse polyelectrolyte brushes studied by self-consistent field theory.

Two complementary self-consistent field theoretical approaches are used to analyze the equilibrium structure of binary and ternary brushes of polyions with different degrees of polymerization. Stratification in binary brushes is predicted: the shorter chains are entirely embedded in the proximal sublayer depleted of end-points of longer chains while the peripheral sublayer contains exclusively terminal segments of longer chains. The boundary between sublayers is enriched with counterions that neutralize the residual charge of the proximal sublayer.

Electrostatic stiffening and induced persistence length for coassembled molecular bottlebrushes.

A self-consistent field analysis for tunable contributions to the persistence length of isolated semiflexible polymer chains including electrostatically driven coassembled deoxyribonucleic acid (DNA) bottlebrushes is presented. When a chain is charged, i.e.

Behavior of Weak Polyelectrolyte Brushes in Mixed Salt Solutions.

Hydrophilic and hydrophobic weak polybasic brushes immersed in aqueous solutions of mixed salt counterions are considered using a mean-field numerical self-consistent field approach. On top of the solvent quality of the polymer, the counterion-solvent interactions are accounted for by implementing Flory-Huggins interaction parameters. We show that ion specificity within the brush can bring about large changes in conformation.

Correction to Force and Scale Dependence of the Elasticity of Self-Assembled DNA Bottle Brushes.

[This corrects the article DOI: 10.1021/acs.macromol.

Sign Switch of Gaussian Bending Modulus for Microemulsions: A Self-Consistent Field Analysis Exploring Scale Invariant Curvature Energies.

Bending rigidities of tensionless balanced liquid-liquid interfaces as occurring in microemulsions are predicted using self-consistent field theory for molecularly inhomogeneous systems. Considering geometries with scale invariant curvature energies gives unambiguous bending rigidities for systems with fixed chemical potentials: the minimal surface Im3m cubic phase is used to find the Gaussian bending rigidity κ[over ¯], and a torus with Willmore energy W=2π^{2} allows for direct evaluation of the mean bending modulus κ. Consistent with this, the spherical droplet gives access to 2κ+κ[over ¯].

Force and Scale Dependence of the Elasticity of Self-Assembled DNA Bottle Brushes.

As a model system to study the elasticity of bottle-brush polymers, we here introduce self-assembled DNA bottle brushes, consisting of a DNA main chain that can be very long and still of precisely defined length, and precisely monodisperse polypeptide side chains that are physically bound to the DNA main chains. Polypeptide side chains have a diblock architecture, where one block is a small archaeal nucleoid protein Sso7d that strongly binds to DNA. The other block is a net neutral, hydrophilic random coil polypeptide with a length of exactly 798 amino acids.

Microphase Segregation of Diblock Copolymers Studied by the Self-Consistent Field Theory of Scheutjens and Fleer.

We used the self-consistent field (SCF) formalism of Scheutjens and Fleer (SF-SCF) to complement existing theoretical investigations on the phase behavior of block copolymer melts. This method employs the freely jointed chain (FJC) model for finite chain length and systematic differences exist compared to the classical SCF predictions. We focus on the critical and hexagonal (HEX) to lamellar (LAM) phase transition region at intermediate and strong segregations.

Unfolding of a comb-like polymer in a poor solvent: translation of macromolecular architecture in the force-deformation spectra.

A numerical self-consistent field modeling approach was employed to study the mechanical unfolding of a globule made by comb-like polymers in a poor solvent with the aim of unraveling how the macromolecular architecture affects the shape of the single-molecule force-deformation curves. We demonstrate that the dependence of the restoring force on the imposed extension of the main chain of the comb-like polymer exhibits a characteristic oscillatory shape in the intermediate deformation range. Theoretical arguments are developed that enable us to relate the shape of the patterns on the force-deformation curves to the molecular architecture (grafting density and length of the side chains) and interaction parameters.

Modeling of Polyelectrolyte Adsorption from Micellar Solutions onto Biomimetic Substrates.

Depositing cationic polyelectrolytes (PEs) from micellar solutions that include surfactants (SU) onto surfaces is a rich, complex, highly relevant, and challenging topic that covers a broad field of practical applications (e.g., from industrial to personal care).

Dendron and Hyperbranched Polymer Brushes in Good and Poor Solvents.

We present a theory of conformational transition triggered by inferior solvent strength in brushes formed by dendritically branched macromolecules tethered to planar, concave, or convex cylindrical and spherical surfaces. In the regime of linear elasticity for brush-forming dendrons, an analytical strong stretching self-consistent field (SS-SCF) approach provides brush conformational properties as a function of solvent strength. A boxlike model is applied to describe the collapse transition in brushes formed by macromolecules with arbitrary treelike topology, including hyperbranched polymers.