Layer-by-layer formation of oligoelectrolyte multilayers: a combined experimental and computational study

TL;DR

This study combines experimental and atomistic simulation methods to analyze the layer-by-layer formation of oligoelectrolyte multilayers, providing detailed insights into their growth and properties at the molecular level.

Contribution

It presents the first integrated experimental and computational approach to study OEM formation, enhancing understanding of multilayer assembly and properties.

Findings

Good agreement between simulation and experimental measurements

Simulations help interpret experimental data more accurately

In situ monitoring reveals kinetic processes not captured by simulations

Abstract

For the first time, the combination of experimental preparation and results of fully atomistic simulations of an oligoelectrolyte multilayer (OEM) made of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) (PDADMAC/PSS) is presented. The layer-by-layer growth was carried out by dipping silica substrates in oligoelectrolyte solutions and was modeled by means of atomistic molecular dynamics simulations with a protocol that mimics the experimental procedure up to the assembly of four layers. Measurements of OEM thickness, surface roughness and amount of adsorbed oligoelectrolyte chains obtained from both approaches are compared. A good agreement between simulated and experimental results was found, with some deviations due to intrinsic limitations of both methods. However, the combination of information extracted from simulations to support the analysis of experimental data can overcome such restrictions and improve the interpretation of experimental results. On the other hand, processes dominated by slower kinetics, like the destabilization of adsorbed layers upon equilibration with the surrounding environment, are out of reach for the simulation modeling approach, but they can be investigated by monitoring in situ the oligoelectrolyte adsorption during the assembly process. This demonstrates how the synergistic use of simulation and experiments improves the knowledge of OEM properties down to the molecular scale.