Complex coacervation and metal-ligand bonding as synergistic design elements for aqueous viscoelastic materials

The application of complex coacervates in promising areas such as coatings and surgical glues requires a tight control of their viscous and elastic behaviour, and a keen understanding of the corresponding microscopic mechanisms. While the viscous, or dissipative, aspect is crucial at pre-setting times and in preventing detachment, elasticity at long waiting times and low strain rates is crucial to sustain a load-bearing joints. The independent tailoring of dissipative and elastic properties proves to be a major challenge that can not be addressed adequately by the complex coacervate motif by itself. We propose a versatile model of complex coacervates with customizable rheological fates by functionalization of polyelectrolytes with terpyridines, which provide transient crosslinks through complexation with metals. We show that the rheology of the hybrid complexes shows distinct footprints of both metal-ligand and coacervate dynamics, the former as a contribution very close to pure Maxwell viscoelasticity, the latter approaching a sticky Rouse fluid. Strikingly, when the contribution of metal-ligand bonds is dominant at long times, the relaxation of the overall complex is much slower than either the "native"coacervate relaxation time or the dissociation time of a comparable non-coacervate polyelectrolyte-metal-ligand complex. We recognize this slowing-down of transient bonds as a synergistic effect that has important implications for the use of complementary transient bonding in coacervate complexes.</p

A mild and quantitative route towards well-defined strong anionic/hydrophobic diblock copolymers:Synthesis and aqueous self-assembly

Block copolymers that accommodate both hydrophobic and ionic elements are interesting materials for numerous applications, such as stabilizing agents, lubricants and proton-exchange membranes. Frequently these copolymers are based on weak polyelectrolytes, but the pH-dependent charge density restricts their use to a limited pH window. Although strong polyelectrolytes do not suffer this problem, the most commonly employed post-modification approach limits the choice of the hydrophobic component, as harsh reaction conditions are usually involved. Moreover, this method often results in incomplete functionalization of the precursor copolymer. To avoid these difficulties a mild route was developed that is based on a hydrophobic protected poly(3-sulfopropyl methacrylate) intermediate that enables the preparation of well-defined strong anionic polyelectrolytes. The potential of this method was demonstrated by synthesizing hydrophobic/strong anionic diblock copolymers, and their self-assembly in aqueous solution was studied

Protected Poly(3-sulfopropyl methacrylate) Copolymers:Synthesis, Stability, and Orthogonal Deprotection

Because of their permanent charge, strong polyelectrolytes remain challenging to characterize, in particular, when they are combined with hydrophobic features. For this reason, they are typically prepared through a postmodification of a fully hydrophobic precursor. Unfortunately, these routes often result in an incomplete functionalization or otherwise require harsh reaction conditions, thus limiting their applicability. To overcome these problems, in this work a strategy is presented that facilitates the preparation of well-defined strong polyanions by starting from protected 3-sulfopropyl methacrylate monomers. Depending on the chemistry of the protecting group, the hydrophobic precursor could be quantitatively converted into a strong polyanion under nucleophilic, acidic, or basic conditions. As a proof of concept, orthogonally protected diblock copolymers were synthesized, selectively deprotected, and allowed to self-assemble in aqueous solution. Further conversion into a fully water-soluble polyanion was achieved by deprotecting the second block as well

Recent Developments and Practical Feasibility of Polymer-Based Antifouling Coatings

While nature has optimized its antifouling strategies over millions of years, synthetic antifouling coatings have not yet reached technological maturity. For an antifouling coating to become technically feasible, it should fulfill many requirements: high effectiveness, long-term stability, durability, ecofriendliness, large-scale applicability, and more. It is therefore not surprising that the search for the perfect antifouling coating has been going on for decades. With the discovery of metal-based antifouling paints in the 1970s, fouling was thought to be a problem of the past, yet its untargeted toxicity led to serious ecological concern, and its use became prohibited. As a response, research shifted focus toward a biocompatible alternative: polymer-based antifouling coatings. This has resulted in numerous advanced and innovative antifouling strategies, including fouling-resistant, fouling-release, and fouling-degrading coatings. Here, these novel and exciting discoveries are highlighted while simultaneously assessing their antifouling performance and practical feasibility

Effect of Polymer Concentration on the Structure and Dynamics of Short Poly(N,N-dimethylaminoethyl methacrylate) in Aqueous Solution:A Combined Experimental and Molecular Dynamics Study

A combined experimental and molecular dynamics (MD) study is performed to investigate the effect of polymer concentration on the zero shear rate viscosity η0 of a salt-free aqueous solution of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), a flexible thermoresponsive weak polyelectrolyte with a bulky 3-methyl-1,1-diphenylpentyl unit as the terminal group. The study is carried out at room temperature (T = 298 K) with relatively short PDMAEMA chains (each containing N = 20 monomers or repeat units) at a fixed degree of ionization (α+ = 100%). For the MD simulations, a thorough validation of several molecular mechanics force fields is first undertaken for assessing their capability to accurately reproduce the experimental observations and established theoretical laws. The generalized Amber force field in combination with the restrained electrostatic potential charge fitting method is eventually adopted. Three characteristic concentration regimes are considered: the dilute (from 5 to 10 wt %), the semidilute (from 10 to 20 wt %), and the concentrated (from 20 to 29 wt %); the latter two are characterized by polymer concentrations cp higher than the characteristic overlap concentration cp*. The structural behavior of the PDMAEMA chains in the solution is assessed by calculating the square root of their mean-square radius of gyration «Rg 2»0.5, the square root of the average square chain end-to-end distance «Ree 2»0.5, the ratio «Ree 2»/«Rg 2», and the persistence length Lp. It is observed that at low polymer concentrations, PDMAEMA chains adopt a stiffer and slightly extended conformation because of excluded-volume effects (a good solvent is considered in this study) and electrostatic repulsions within the polymer chains. As the polymer concentration increases above 20 wt %, the PDMAEMA chains adopt more flexible conformations, as the excluded-volume effects seize and the charge repulsion within the polymer chains subsides. The effect of total polymer concentration on PDMAEMA chain dynamics in the solution is assessed by calculating the orientational relaxation time τc of the chain, the center-of-mass diffusion coefficient D, and the zero shear rate viscosity η0; the latter is also measured experimentally here and found to be in excellent agreement with the MD predictions.</p

Water-Processable, Stretchable, and Ion-Conducting Coacervate Fibers from Keratin Associations with Polyelectrolytes

[Image: see text] Keratin is one of the most abundant biopolymers, produced on a scale of millions of tons per year but often simply discarded as waste. Due to its abundance, biocompatibility, and excellent mechanical properties, there is an extremely high interest in developing protocols for the recycling of keratin and its conversion into protein-based materials. In this work, we describe a novel protocol for the conversion of keratin from wool into hybrid fibers. Our protocol uses a synthetic polyanion, which undergoes complex coacervation with keratin, leading to a viscous liquid phase that can be used directly as a dope for dry-spinning. The use of polyelectrolyte complexation allows us to use all of the extracted keratin, unlike previous works that were limited to the fraction with the highest molecular weight. The fibers prepared by this protocol show excellent mechanical properties, humidity responsiveness, and ion conductivity, which makes them promising candidates for applications as a strain sensor