Polyelectrolytes are an important class of polymeric materials and are increasingly used in complex industrial formulations. A core use of these materials is in mixtures with surfactants, where a combination of hydrophobic and electrostatic interactions drives unique solution behavior and structure formation. In this review, we apply a molecular level perspective to the broad literature on polyelectrolyte-surfactant complexes, discussing explicitly the hydrophobic and electrostatic interaction contributions to polyelectrolyte surfactant complexes (PESCs), as well as the interplay between the two molecular interaction types. These interactions are sensitive to a variety of solution conditions, such as pH, ionic strength, mixing procedure, charge density, etc. and these parameters can readily be used to control the concentration at which structures form as well as the type of structure in the bulk solution.

The ideal bone scaffold harnesses the body's ability to regenerate bone in critical size defects. A potential strategy to design the ideal bone scaffold is to mimic the natural structure of bone at the molecular level. The orientation and spatial distribution of nanocrystals in the organic matrix are two important and distinctive structural characteristics associated with natural bone. There has yet to be a synthetic system or scaffold that is able to control both the spatial distribution and orientation of the hydroxyapatite crystalline structure. To mimic the unique hybrid structure of natural bone using synthetic materials, there have been a number of reported approaches to control the mineral nanocrystal orientation on synthetic scaffolds. However, the spatial distribution of minerals is challenging to reproduce in a biomimetic manner. Herein we report using block copolymer-decorated polymer nanofibers to achieve biomineralized fibrils with precise control of both mineral crystal orientation and spatial distribution. We show that the crystallization of poly(caprolactone)-b-poly(acrylic acid) block copolymer on poly(caprolactone) nanofibers resulted in a unique shish kebab structure that significantly enhances the mechanical properties of the nanofibers, and is cytocompatible to L-929 mouse fibroblast cells. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1786-1798, 2017.

Polyelectrolytes are used in paper manufacturing to increase flocculation and water drainage and improve mechanical properties. In this study, we examine the interaction between charged cellulosic nanomaterials and polyelectrolyte complex coacervates of weak polyelectrolytes, polyacrylic acid salt, and polyallylamine hydrochloride. We observe that by changing the order of addition of the polyelectrolytes to cellulose nanofibers (CNFs), we can tune the interactions between the materials, which in turn changes the degree of association of the coacervates to the CNFs and the rate at which they aggregate. Importantly for the papermaking process, when adding the polyelectrolytes sequentially to the CNFs, we found faster aggregation to the fibers and lower water retention values compared to those when preformed coacervates or CNFs by themselves were used. Coarse-grain molecular dynamic simulations further support the fundamental mechanism of aggregation by taking into consideration the interaction between cellulose and the complexes at the molecular level. The simulations corroborate the experimental observations by showing the importance of strong electrostatic interactions in aggregate formation.

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