The multi-scale polarizable pseudo-particle solvent coarse-grained approach: From NaCl salt solutions to polyelectrolyte hydration.

We discuss key parameters that affect the reliability of hybrid simulations in the aqueous phase based on an efficient multi-scale coarse-grained polarizable pseudo-particle approach, denoted as pppl, to model the solvent water, whereas solutes are modeled using an all atom polarizable force field. Among those parameters, the extension of the solvent domain (SD) at the solute vicinity (domain in which each solvent particle corresponds to a single water molecule) and the magnitude of solute/solvent short range polarization damping effects are shown to be pivotal to model NaCl salty aqueous solutions and the hydration of charged systems, such as the hydrophobic polyelectrolyte polymer that we have recently investigated [Masella et al., J. Chem. Phys. 155, 114903 (2021)]. Strong short range damping is pivotal to simulate aqueous salt NaCl solutions at moderate concentration (up to 1.0M). The SD extension (as well as short range damping) has a weak effect on the polymer conformation; however, it plays a pivotal role in computing accurate polymer/solvent interaction energies. As the pppl approach is up to two orders of magnitude computationally more efficient than all atom polarizable force field methods, our results show it to be an efficient alternative route to investigate the equilibrium properties of complex charged molecular systems in extended chemical environments.

Chitosan Polysaccharides from a Polarizable Multiscale Approach.

We report simulations of chitosan polysaccharides in the aqueous phase, at infinite dilute conditions and zero ionic strength. Those simulations are performed by means of a polarizable multiscale modeling scheme that relies on a polarizable all atom force field to model solutes and on a polarizable solvent coarse grained approach. Force field parameters are assigned only from quantum chemistry ab initio data. We simulate chitosan monomer units, dimers and 50-long chains. Regarding the 50-long chains we simulate three sets of ten randomly built chain replica at three different pH conditions (corresponding to different chain protonation states, the chain degree of deacetylation is 85%). Our simulations show the persistence length of 50-long chitosan chains at strong acidic conditions (pH <5) to be 24 ± 2 nm (at weak/negligible ionic strength conditions), and to be 1 order of magnitude shorter at usual pH conditions. Our simulation data support the most recent simulation and experimental studies devoted to chitosan polysaccharides in the aqueous phase.

Shearing friction behaviour of synthetic polymers compared to a functionalized polysaccharide on biomimetic surfaces: models for the prediction of performance of eco-designed formulations.

The substitution of natural, bio-based and/or biodegradable polymers for those of petrochemical origin in consumer formulations has become an active area of research and development as the sourcing and destiny of material components becomes a more critical factor in product design. These polymers often differ from their petroleum-based counterparts in topology, raw material composition and solution behaviour. Effective and efficient reformulation that maintains comparable cosmetic performance to existing products requires a deep understanding of the differences in frictional behaviour between polymers as a function of their molecular structure. In this work, we simulate the tribological behaviour of three topologically distinct polymers in solution with surfactants and in contact with hair-biomimetic patterned surfaces. We compare a generic functionalized polysaccharide to two performant polymers used in shampoo formulations: a strongly positively charged polyelectrolyte and a zwitterionic copolymer. Topological differences are expected to affect rheological properties, as well as their direct interaction with structured biological substrates. Using a refined Martini-style coarse-grained model we describe the polymer-dependent differences in aggregation behaviour as well as selective interactions with a biomimetic model hair surface. Additionally, we introduce a formalism to characterize the response of the solution to shear as an initial study on lubrication properties, which define the sensorial performance of these systems in cosmetics (i.e., manageability, touch, etc.). The tools and techniques presented in this work illustrate the strength of molecular simulation in eco-design of formulation as a complement to experiment. These efforts help advance our understanding of how we can relate complex atomic-scale solution behaviour to relevant macroscopic properties. We expect these techniques to play an increasingly important role in advancing strategies for green polymer formulation design by providing an understanding for how new polymers could reach and even exceed the level of performance of existing polymers.

Study of the Dilution-Induced Deposition of Concentrated Mixtures of Polyelectrolytes and Surfactants.

Mixtures of polyelectrolytes and surfactants are commonly used in many technological applications where the challenge is to provide well-defined modifications of the surface properties, as is the case of washing formulations in cosmetics. However, if contemporary experimental and theoretical methods can provide insights on their behavior in concentrated formulations, less is known on their behavior under practical use conditions, e.g., under dilution and vectorization of deposits. This makes it difficult to make predictions for specific performance, as, for example, good hair manageability after a shampoo or a comfortable sensorial appreciation after a skin cleanser. This is especially important when considering the formulation of new, more eco-friendly formulations. In this work, a detailed study of the phase separation process induced by dilution is described, as well as the impact on the deposition of conditioning material on negatively charged surfaces. In order to gain a more detailed physical insight, several polyelectrolyte-surfactant pairs, formed by two different polymers and five surfactants that, although non-natural or eco-friendly, can be considered as models of classical formulations, have been studied. The results evidenced that upon dilution the behavior, and hence its deposition onto the surface, cannot be predicted in terms of the behavior of simpler pseudo-binary (mixtures of a polymer and a surfactant) or pseudo-ternary mixtures (two polymers and a surfactant). In many cases, phase separation was observed for concentrations similar to those corresponding to the components in some technological formulations, whereas the latter appeared as monophasic systems. Therefore, it may be assumed that the behavior in multicomponent formulations is the result of a complex interplay of synergistic interactions between the different components that will require revisiting when new, more eco-sustainable ingredients are considered.

Hybrid polarizable simulations of a conventional hydrophobic polyelectrolyte. Toward a theoretical tool for green science innovation.

Hybrid modeling approaches based on all-atom force fields to handle a solute and coarse-grained models to account for the solvent are promising numerical tools that can be used to understand the properties of large and multi-components solutions and thus to speed up the development of new industrial products that obey the standard of green and sustainable chemistry. Here, we discuss the ability of a full polarizable hybrid approach coupled to a standard molecular dynamics scheme to model the behavior in the aqueous phase and at infinite dilution conditions of a standard hydrophobic polyelectrolyte polymer whose charge is neutralized by explicit counterions. Beyond the standard picture of a polyelectrolyte behavior governed by an interplay between opposite intra-polyelectrolyte and inter-polyelectrolyte/counterion Coulombic effects, our simulations show the key role played by both intra-solute polarization effects and long range solute/solvent electrostatics to stabilize compact globular conformations of that polyelectrolyte. Our full polarizable hybrid modeling approach is thus a new theoretical tool well suited to be used in digital strategies for accelerating innovation for green science, for instance.

Dendritic growth of protein gel in the course of sweat pore plugging by aluminium salts under physiological conditions.

Are aluminium ions unavoidable in antiperspirants? To answer this question, we present confocal microscopy images of dendritic plugs appearing in sweat flowing across a microfluidic channel in the presence of aluminium salts. By comparing with numerical simulations, we identify the mechanisms forming this structured protein gel inside the pore.

Adsorption and Desorption of Polymers on Bioinspired Chemically Structured Substrates.

Natural biological surfaces exhibit interesting properties due to their inhomogeneous chemical and physical structure at the micro- and nanoscale. In the case of hair or skin, this also influences how waterborne macromolecules ingredients will adsorb and form cosmetically performing deposits (i.e., shampoos, cleansers, etc.). Here, we study the adsorption of hydrophilic flexible homopolymers on heterogeneous, chemically patterned substrates that represent the surface of the hair by employing coarse-grained molecular dynamics simulations. We develop a method in which the experimental images of the substrate are used to obtain information about the surface properties. We investigate the polymer adsorption as a function of polymer chain length and polymer concentration spanning both dilute and semidilute regimes. Adsorbed structures are quantified in terms of trains, loops, and tails. We show that upon increasing polymer concentration, the length of tails and loops increases at the cost of monomers belonging to trains. Furthermore, using an effective description, we probe the stability of the resulting adsorbed structures under a linear shear flow. Our work is a first step toward developing models of complex macromolecules interacting with realistic biological surfaces, as needed for the development of more ecofriendly industrial products.

Surface science of cosmetic substrates, cleansing actives and formulations.

The development of shampoo and cleansing formulations in cosmetics is at a crossroads due to consumer demands for better performing, more natural products and also the strong commitment of cosmetic companies to improve the sustainability of cosmetic products. In order to go beyond traditional formulations, it is of great importance to clearly establish the science behind cleansing technologies and appreciate the specificity of cleansing biological surfaces such as hair and skin. In this review, we present recent advances in our knowledge of the physicochemical properties of the hair surface from both an experimental and a theoretical point of view. We discuss the opportunities and challenges that newer, sustainable formulations bring compared to petroleum-based ingredients. The inevitable evolution towards more bio-based, eco-friendly ingredients and sustainable formulations requires a complete rethink of many well-known physicochemical principles. The pivotal role of digital sciences and modelling in the understanding and conception of new ingredients and formulations is discussed. We describe recent numerical approaches that take into account the specificities of the hair surface in terms of structuration, different methods that study the adsorption of formulation ingredients and finally the success of new data-driven approaches. We conclude with practical examples on current formulation efforts incorporating bio-surfactants, controlling foaming and searching for new rheological properties.

Real time observation of the interaction between aluminium salts and sweat under microfluidic conditions.

Aluminium salts such as aluminium chlorohydrate (ACH) are the active ingredients of antiperspirant products. Their mechanism of action involves a temporary and superficial plugging of eccrine sweat pores at the skin surface. We developed a microfluidic system that allows the real time observation of the interactions between sweat and ACH in conditions mimicking physiological sweat flow and pore dimensions. Using artificial sweat containing bovine serum albumin as a model protein, we performed experiments under flowing conditions to demonstrate that pore clogging results from the aggregation of proteins by aluminium polycations at specific location in the sweat pore. Combining microfluidic experiments, confocal microscopy and numerical models helps to better understand the physical chemistry and mechanisms involved in pore plugging. The results show that plugging starts from the walls of sweat pores before expanding into the centre of the channel. The simulations aid in explaining the influence of ACH concentration as well as the impact of flow conditions on the localization of the plug. Altogether, these results outline the potential of both microfluidic confocal observations and numerical simulations at the single sweat pore level to understand why aluminium polycations are so efficient for sweat channel plugging.

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. An application wherein it is believed that autophobic wetting is counteracted by such a set of wetting additives is found in an antidandruff shampoo formulation. We have experimental results that show thick deposits onto hydrophobic hair surfaces by administration of the antidandruff shampoo. The complementary modeling of such a system suggests that the active ingredient plays the role of the co-solvent additive. As significant amounts of the co-solvent additives are needed to approach the completely wet state, the formulation naturally brings large amounts of active ingredient to the root of the hair where its presence is required.

Self-Consistent Mean Field Calculations of Polyelectrolyte-Surfactant Mixtures in Solution and upon Adsorption onto Negatively Charged Surfaces.

Self-Consistent Mean-Field Calculations (SCF) have provided a semi-quantitative description of the physico-chemical behavior of six different polyelectrolyte-surfactant mixtures. The SCF calculations performed showed that both the formation of polymer-surfactant in bulk and the adsorption of the formed complexes onto negatively-charged surfaces are strongly affected by the specific nature of the considered systems, with the polymer-surfactant interactions playing a central role in the self-assembly of the complexes that, in turn, affects their adsorption onto interfaces and surfaces. This work evidences that SCF calculations are a valuable tool for deepening on the understanding of the complex physico-chemical behavior of polyelectrolyte-surfactant mixtures. However, it is worth noting that the framework obtained on the basis of an SCF approach considered an equilibrium situation which may, in some cases, be far from the real situation appearing in polyelectrolyte-surfactant systems.

Effect of molecular structure of eco-friendly glycolipid biosurfactants on the adsorption of hair-care conditioning polymers.

Pseudo-binary mixtures of different glycolipids, four different rhamnolipids (RL) and an alkyl polyglucoside (APG), with poly(diallyl-dimethylammonium chloride) (PDADMAC) have been studied in relation to their adsorption onto negatively charged surfaces to shed light on the impact of the molecular structure of surfactants from natural sources (instead of synthetic surfactant, such as sodium laureth sulfate) on the adsorption of hair-conditioning polymers. For this purpose, the self-assembly of such mixtures in aqueous solution and their adsorption onto negatively charged surfaces mimicking the negative charge of damaged hair fibres have been studied combining experiments and self-consistent field (SCF) calculations. The results show that the specific physico-chemical properties of the surfactants (charge, number of sugar rings present in surfactant structure and length of the hydrocarbon length) play a main role in the control of the adsorption process, with the adsorption efficiency and hydration being improved in relation to conventional sulfate-based systems for mixtures of PDADMAC and glycolipids with the shortest alkyl chains. SCF calculations and Energy Dispersive X-Ray Spectroscopy (EDS) analysis on real hair confirmed such observations. The results allow one to assume that the characteristic of the surfactants, especially rhamnolipids, conditions positively the adsorption potential of polyelectrolytes in these model systems. This study provides important insights on the mechanisms underlying the performance of more complex but eco-friendly washing formulations.

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). The role of the molecular architecture of the constituents of the PEs are often overruled, or at least and either, underestimated in regard to the surface properties. In this work, we aim to evaluate the effect of a model biomimetic surface that shares the key characteristics of the extreme surface of hair and its concomitant chemo- and physisorbed properties onto the deposition of a complex PEs:SU system. To tackle out the effect of the molecular architecture of the PEs, we consider (i) a purely linear and hydrophilic PE (P100) and (ii) a PE with lateral amphiphilic chains (PegPE). Using numerical self-consistent field calculations, we show that the architecture of the constituents interfere with the surface properties in a nonintuitive way such that, depending on the amphiphilicity and hydrophilicity of the PEs and the hydrophobicity of the surface, a re-entrant adsorbing transition can be observed, the lipid coverage of the model hair surface being the unique control parameter. Such a behavior is rationalized by the anticooperative associative properties of the coacervate micelles in solution, which is also controlled by the architecture of the PEs and SU. We now expect that PEs adsorption, as a rule, is governed by the molecular details of the species in solution as well as the surface specificities. We emphasize that molecular realistic modeling is essential to rationalize and optimize the adsorption process of, for example, polymer conditioning agents in water-rinsed cosmetic or textile applications.

Poly(N-isopropylacrylamide)-Based Mixed Brushes: A Computer Simulation Study.

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) polymer brushes of fixed molecular weight and grafting density are modeled in the framework of a coarse-grained model with soft, nonbonded interactions and an implicit solvent. This model has been developed to address experimentally relevant, large invariant degrees of polymerization, and nonbonded interactions are expressed via a third-order (virial) expansion of the equation of state. The choice of interaction parameters is intended to mimic the swelling behavior of PNIPAM in water as the temperature increases toward the lower critical solution temperature (T(LCST)). Results of molecular dynamics simulations for one component brushes are compared to experimental data. Mixed brushes incorporating small and large amounts of grafted poly(ethylene glycol) polymers are then considered. The effects of mixing polymer components on the response of the mixed brushes to temperature changes are monitored, and the results are compared to experimental data. In the end, two design principles for biomolecule triggering using temperature-sensitive mixed polymer brushes with functional and switchable end-groups are proposed and studied. This work is in favor of establishing qualitative rules for the design, optimization, and comprehension of binary polymer brushes for bioengineering purposes.

Polymer chain generation for coarse-grained models using radical-like polymerization.

A versatile method is proposed to generate configurations of coarse-grained models for polymer melts. This method, largely inspired by chemical "radical polymerization," is divided in three stages: (i) nucleation of radicals (reacting molecules caching monomers), (ii) growth of chains within a solvent of monomers and (iii) termination: annihilation of radicals and removal of residual monomers. The main interest of this method is that relaxation is performed while chains are generated. Pure mono and polydisperse polymer melts are generated and compared to the configurations generated by the push off method from Auhl et al. [J. Chem. Phys. 119, 12718 (2003)]. A detailed study of the static properties (radius of gyration, mean square internal distance, entanglement length) confirms that the radical-like polymerization technique is suitable to generate equilibrated melts. Moreover, the method is flexible and can be adapted to generate nanostructured polymers, namely, diblock and triblock copolymers.