Abstract
Surface functionalization with end-tethered weak polyelectrolytes (PE) is a versatile way to modify and control surface properties, given their ability to alter their degree of charge depending on external cues like pH and salt concentration. Weak PEs find usage in a wide range of applications, from colloidal stabilization, lubrication, adhesion, wetting to biomedical applications such as drug delivery and theranostics applications. They are also ubiquitous in many biological systems. Here, we present an overview of some of the main theoretical methods that we consider key in the field of weak PE at interfaces. Several applications involving engineered nanoparticles, synthetic and biological nanopores, as well as biological macromolecules are discussed to illustrate the salient features of systems involving weak PE near an interface or under (nano)confinement. The key feature is that by confining weak PEs near an interface the degree of charge is different from what would be expected in solution. This is the result of the strong coupling between structural organization of weak PE and its chemical state. The responsiveness of engineered and biological nanomaterials comprising weak PE combined with an adequate level of modeling can provide the keys to a rational design of smart nanosystems.
Highlights
The use of end-tethered polymers and polyelectrolytes has been ubiquitous in a wide range of applications
We want to present an overview of some of the theoretical methods that we consider key in the field of weak PE at interfaces, to enable a better understanding of the various theoretical approaches
We presented an overview of some of the main theoretical methods that we consider key in the field of weak PE at interfaces, as well as salient applications of them in the study of engineered NPs and nanopores
Summary
The use of end-tethered polymers and polyelectrolytes has been ubiquitous in a wide range of applications. Theoretical investigations into the behavior of weak polyelectrolyte layers is more recent and its theoretical understanding is less complete These methods use previous theoretical approaches developed to investigate neutral polymers and strong PE layers as a starting point. They include theoretical approaches such as scaling theory, analytical and numerical self-consistent field theory, and density functional theory. These approaches inherit the advantages and weak points of those neutral polymer theories and add to them the complexity of electrostatic and chemical interactions.
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