The interactions of proteins and polyelectrolytes lead to diverse applications in separations, delivery and wound repair, and are thus of interest to scientists in e.g. (a) glycobiology, (b) tissue engineering, (c) biosensing, and (d) pharmacology. This breadth is accompanied by an assortment of contexts and models in which polyelectrolytes are seen as (a) protein cognates assisting in complex cellular roles, (b) surrogates for the extracellular matrix, mimicking its hydration, mechanical and sequestering properties, (c) benign hosts that gently entrap, deposit and tether protein substrate specificity, and (d) selective but non-specific agents that modify protein solubility. Unsurprisingly, this literature is somewhat segregated by objectives and paradigms. We hope this review, which emphasizes publications over the last 8 years, represents and also counterbalances that divergence. An ongoing theme is the role of electrostatics, and we show how this leads to the variety of physical forms taken by protein–polyelectrolyte complexes. We present approaches towards analysis and characterization, motivated by the goal of structure–property elucidation. Such understanding should guide in applications, our third topic. We present recent developments in modeling and simulations of protein–polyelectrolyte systems. We close with a prospective on future developments in this field.

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Protein–polyelectrolyte interactions

Complex coacervation is an associative, liquid–liquid phase separation that can occur in solutions of oppositely-charged macromolecular species, such as proteins, polymers, and colloids. This process results in a coacervate phase, which is a dense mix of the oppositely-charged components, and a supernatant phase, which is primarily devoid of these same species. First observed almost a century ago, coacervates have since found relevance in a wide range of applications; they are used in personal care and food products, cutting edge biotechnology, and as a motif for materials design and self-assembly. There has recently been a renaissance in our understanding of this important class of material phenomena, bringing the science of coacervation to the forefront of polymer and colloid science, biophysics, and industrial materials design. In this review, we describe the emergence of a number of these new research directions, specifically in the context of polymer–polymer complex coacervates, which are inspired by a number of key physical and chemical insights and driven by a diverse range of experimental, theoretical, and computational approaches.

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Recent progress in the science of complex coacervation

This Perspective outlines recent advances concerning the formation and potential uses of block copolymer micelles, a class of soft-matter-based nanoparticles of growing importance. As a result of rapidly expanding interest since the mid-1990s, substantial advances have been reported in terms of the development of morphological diversity, structural complexity, control over micelle dimensions, scale-up, and applications in a range of areas from nanocomposites to nanomedicine.

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50th Anniversary Perspective: Functional Nanoparticles from the Solution Self-Assembly of Block Copolymers

The rapid and robust adhesion of marine mussels to diverse solid surfaces in wet environments is mediated by the secreted mussel adhesive proteins which are abundant in a catecholic amino acid, l-3,4-dihydroxyphenylalanine (Dopa). Over the last two decades, enormous efforts have been devoted to the development of synthetic mussel-inspired adhesives with water-resistant adhesion and cohesion properties by modifying polymer systems with Dopa and its analogues. In the present review, an overview of the unique features of various mussel foot proteins is provided in combination with an up-to-date understanding of catechol chemistry, which contributes to the strong interfacial binding via balancing a variety of covalent and noncovalent interactions including oxidative cross-linking, electrostatic interaction, metal-catechol coordination, hydrogen bonding, hydrophobic interactions and π-π/cation-π interactions. The recent developments of novel Dopa-containing adhesives with on-demand mechanical properties and other functionalities are then summarized under four broad categories: viscous coacervated adhesives, soft adhesive hydrogels, smart adhesives, and stiff adhesive polyesters, where their emerging applications in engineering, biological and biomedical fields are discussed. Limitations of the developed adhesives are identified and future research perspectives in this field are proposed.

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Recent progress in synthesis and application of mussel-inspired adhesives

There has been increasing interest in complex coacervates for deriving and transporting biomaterials. Complex coacervates are a dense, polyelectrolyte-rich liquid that results from the electrostatic complexation of oppositely charged macroions. Coacervates have long been used as a strategy for encapsulation, particularly in food and personal care products. More recent efforts have focused on the utility of this class of materials for the encapsulation of small molecules, proteins, RNA, DNA, and other biomaterials for applications ranging from sensing to biomedicine. Furthermore, coacervate-related materials have found utility in other areas of biomedicine, including cartilage mimics, tissue culture scaffolds, and adhesives for wet, biological environments. Here, we discuss the self-assembly of complex coacervate-based materials, current challenges in the intelligent design of these materials, and their utility applications in the broad field of biomedicine. WIREs Nanomed Nanobiotechnol 2017, 9:e1442. doi: 10.1002/wnan.1442 For further resources related to this article, please visit the WIREs website.

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Complex coacervate-based materials for biomedicine.

For the last decades, amphiphilic block copolymers have been at the focus of extensive scientific interest, due to their unique properties and numerous potential applications. Their technological potential evolves from their ability to self-assemble into a plethora of morphologically diverse nanostructures such as micelles, polymersomes, cylinders and others. In this chapter, we discuss the basic principles governing amphiphilic block copolymer self-organisation in solutions and the variety of morphologies observed so far, as well as the experimental techniques available for characterising such nanostructures. Some representative examples of self-assembly from nonionic and ionic amphiphilic block copolymers of different macromolecular architectures are also presented.

Self-Assembly of Amphiphilic Block Copolymers in Selective Solvents

https://onlinelibrary.wiley.com/doi/pdf/10.1002/pol.20210430

Block copolymer solution self-assembly: Recent advances, emerging trends, and applications

Complexation of lysozyme with poly(sodium(sulfamate-carboxylate)isoprene).

Complexation of cationic-neutral block polyelectrolyte with insulin and in vitro release studies.

Micellar and fractal aggregates formed by two triblock terpolymers with different arrangements of one charged, one neutral hydrophilic and one hydrophobic block

Maria Karayianni

Papers

Self-Assembly of Amphiphilic Block Copolymers in Selective Solvents

Block copolymer solution self-assembly: Recent advances, emerging trends, and applications

Complexation of lysozyme with poly(sodium(sulfamate-carboxylate)isoprene).

Complexation of cationic-neutral block polyelectrolyte with insulin and in vitro release studies.

Micellar and fractal aggregates formed by two triblock terpolymers with different arrangements of one charged, one neutral hydrophilic and one hydrophobic block