Abstract: Lignosulfonates are bio-based surfactants and specialty chemicals, which are generated by breaking the near-infinite lignin network during sulfite pulping of wood. Due to their amphiphilic nature, lignosulfonates are used in manifold applications such as plasticizer, dispersant, and stabilizer formulations. Function and performance are determined by their behavior in aqueous solution and at surfaces and interfaces, which is in turn imposed by the chemical make-up. This review hence summarizes the efforts made into delineating the physicochemical properties of lignosulfonates, while also relating to their composition and structure. Lignosulfonates are randomly branched polyelectrolytes with abundant sulfonate and carboxylic acid groups to ensure water-solubility. In aqueous solution, their conformation, colloidal state, and adsorption at surfaces or interfaces can be affected by a range of parameters, such as pH, concentration of other electrolytes, temperature, and the presence of organic solvents. These parameters may also affect the adsorption behavior, which reportedly follows Langmuir isotherm and pseudo second-order kinetics. The relative hydrophobicity, as determined by hydrophobic interaction chromatography, is an indicator that can help to relate composition and behavior of lignosulfonates. More hydrophobic materials have been found to exhibit a lower charge density. This may improve dispersion stabilization, but it can also be disadvantageous if an electrokinetic charge needs to be introduced at solid surfaces or if precipitation due to salting out is an issue. In addition, the monolignol composition, molecular weight distribution, and chemical modification may affect the physicochemical behavior of lignosulfonates. In conclusion, the properties of lignosulfonates can be tailored by controlling aspects such as the production parameters, fractionation, and by subsequent modification. Recent developments have spawned a magnitude of products and technologies, which is also reflected in the wide variety of possible application areas.

Abstract: Cations are crucial components in emerging functional polyelectrolytes for a myriad of applications. Rapid development in this area necessitates the exploration of new cations with advanced properties. Herein we describe a combination of computational and experimental design of cobaltocene metallo-cations that have distinct electronic and redox properties. One of the direct outcomes on the first synthesis of a complete set of cation derivatives is to discover highly stable cations, which are further integrated to construct metallo-polyelectrolytes as anion-exchange membranes in solid-state alkaline fuel cells. The device performance of these polyelectrolytes under highly basic and oxidative environments is competitive with many organo-polyelectrolytes.

Abstract: Metal-organic frameworks (MOFs) are diffusely defined as a promising class of porous material for uranium extraction from seawater, but there are still challenges in their stability and anti-biofouling performance. Herein, a water-stable and anti-biofouling ZIF-67/SAP0.45 composite hydrogel was reported by the sequential processes of electrostatic interactions between the oppositely charged polymer, ionic gelation, and template growth of ZIF-67 crystals. Entanglement of positively charged polyethyleneimine (PEI) and negatively charged sodium alginate (SA) polymer chains provided external porosities, anti-biofouling properties, and mechanical support for the hydrogels and further reduced the possibility of ZIF-67 aggregation. The neutral composite hydrogel possessed the least Nitzschia on the surface after 7 days contact, which endows the adsorbent with a high uranium uptake capacity of 2107.87 ± 41.64 μg g-1 at 1 mg L-1 uranium-containing seawater with 8.6 × 105 mL-1 Nitzschia. Additionally, this adsorbent showed water stability with an uranium uptake capacity of 232.88 ± 8.02 mg g-1 even after five adsorption-desorption cycles because of the excellent preparation method. Benefitting from the distinctive hierarchical structure and large accessible surface area, the resultant adsorbent achieved a high uranium capacity of 6.99 ± 0.26 mg g-1 in real seawater. This flexible and scalable approach made the MOF/SAP composite hydrogel a highly desirable uranium adsorbent.

Abstract: Nonsolvent induced phase separation (NIPS) is the most common approach to produce polymeric membranes. Unfortunately, NIPS relies heavily on aprotic organic solvents like N-methyl-pyrrolidone. These solvents are unsustainable, repro-toxic for humans and are therefore becoming increasingly restricted within the European Union. A new and sustainable method, aqueous phase separation (APS), is reported that eliminates the use of organic solvents. A homogeneous solution of two polyelectrolytes, the strong polyanion poly(sodium 4-styrenesulfonate) (PSS) and the weak polycation poly(allylamine hydrochloride) (PAH), is prepared at high pH, where PAH is uncharged. Immersing a film of this solution in a low pH bath charges the PAH and results in a controlled precipitation, forming a porous water-insoluble polyelectrolyte complex, a membrane. Pore sizes can be tuned from micrometers to just a few nanometers, and even to dense films, simply by tuning the polyelectrolyte concentrations, molecular weights, and by changing the salinity of the bath. This leads to excellent examples of microfiltration, ultrafiltration, and nanofiltration membranes. Polyelectrolyte complexation induced APS is a viable and sustainable approach to membrane production that provides excellent control over membrane properties and even allows new types of separations.

Abstract: Tackling membrane wetting is an ongoing challenge for large-scale applications of membrane distillation (MD). Herein, composite Janus MD membranes comprising an ultrathin dense hydrophilic layer are developed by layer-by-layer assembling cationic polyethyleneimine and anionic poly(sodium 4-styrenesulfonate) polyelectrolytes on a hydrophobic polyvinylidene fluoride substrate. Using surfactant-containing saline water as the feed with low surface tension, experiments reveal that the number of polyelectrolyte layers, rather than surface wettability or surface charge, determines the anti-wetting performance of the composite Janus membranes. More deposited layers yield higher wetting resistance. With the aid of positron annihilation spectroscopy, this study, for the first time, demonstrates the origin of the excellent wetting resistance of the composite Janus membranes. The effective pore size of the polyelectrolyte multilayer decreases with an increase in the number of the deposited layer. The membrane with an ultrathin hydrophilic multilayer of 48 nm has a sufficiently small pore size to sieve out surfactant molecules from the feed solution via a size exclusion mechanism, thus protecting the hydrophobic substrate from being wetted by the low-surface-tension feed water. This study may pave the way for developing next-generation anti-wetting Janus membranes for robust membrane distillation.

Abstract: Highly charged intrinsically disordered proteins can form complexes with very high affinity in which both binding partners fully retain their disorder and dynamics, exemplified by the positively charged linker histone H1.0 and its chaperone, the negatively charged prothymosin α. Their interaction exhibits another surprising feature: The association/dissociation kinetics switch from slow two-state-like exchange at low protein concentrations to fast exchange at higher, physiologically relevant concentrations. Here we show that this change in mechanism can be explained by the formation of transient ternary complexes favored at high protein concentrations that accelerate the exchange between bound and unbound populations by orders of magnitude. Molecular simulations show how the extreme disorder in such polyelectrolyte complexes facilitates (i) diffusion-limited binding, (ii) transient ternary complex formation, and (iii) fast exchange of monomers by competitive substitution, which together enable rapid kinetics. Biological polyelectrolytes thus have the potential to keep regulatory networks highly responsive even for interactions with extremely high affinities.

Abstract: The aim of our study was to develop a novel method for the preparation of polymeric core-shell nanoparticles loaded with various actives for biomedical applications. Poly(caprolactone) (PCL), poly(lactic acid) (PLA) and poly(lactide-co-glycolide) (PLGA) nanoparticles were prepared using the spontaneous emulsification solvent evaporation (SESE) method. The model active substance, Coumarin-6, was encapsulated into formed polymeric nanoparticles, then they were modified/functionalized by multilayer shells' formation. Three types of multilayered shells were formed: two types of polyelectrolyte shell composed of biocompatible and biodegradable polyelectrolytes poly-L-lysine hydrobromide (PLL), fluorescently-labeled poly-L-lysine (PLL-ROD), poly-L-glutamic acid sodium salt (PGA) and pegylated-PGA (PGA-g-PEG), and hybrid shell composed of PLL, PGA, and SPIONs (superparamagnetic iron oxide nanoparticles) were used. Multilayer shells were constructed by the saturation technique of the layer-by-layer (LbL) method. Properties of our polymeric core-shell nanoparticle were optimized for bioimaging, passive and magnetic targeting.

Abstract: Polyelectrolyte complexes (PECs) offer enormous material tunability and desirable functionalities, and consequently have found broad utility in biomedical and material industries. While poly(acryli...

Abstract: Polyelectrolytes self-assembly is developing rapidly as a fascinating family of functional membrane fabrication strategies with the ability to modulate the architectures and physical–chemical characteristics of membranes at the molecular level. Research on polyelectrolytes self-assembly is motivated by the flexible choice of functional groups and processing technologies as well as the synergy of the charge and nanostructure control, thus allowing extensive applications of polyelectrolytes-based functional membranes for precise separation. Herein, an account of recent advances in the design and performance evaluation of polyelectrolytes self-assembled membranes is provided. First, the rational selection of polyelectrolytes is outlined, with a focus on selection criteria and structure–performance relationship, which are crucial factors for membrane fabrication. Then, the different design strategies of polyelectrolytes self-assembled membranes are introduced, comprising well-established and newly emerging methods. Next, the separation-related applications so far pursued by polyelectrolytes self-assembled membranes are itemized, covering gas separation and liquid separation. Their potential utility targeting on challenging separation fields such as decontamination, organic micropollutants removal, and resources recovery, is emphatically highlighted. Looking forward, exploiting the high flexibility and feasibility of certain polyelectrolytes self-assembly techniques is put into perspective for niche applications that are not easily achievable by other polymers. Overall, critical insights are provided for the materials science and membrane communities to navigate better exploring the potential of polyelectrolytes self-assembly for developing advanced functional membranes.

Abstract: Polymeric membranes are used on very large scales for drinking water production and kidney dialysis, but they are nearly always prepared by using large quantities of unsustainable and toxic aprotic solvents. In this study, a water-based, sustainable, and simple way of making polymeric membranes is presented without the need for harmful solvents or extreme pH conditions. Membranes were prepared from water-insoluble polyelectrolyte complexes (PECs) via aqueous phase separation (APS). Strong polyelectrolytes (PEs), poly(sodium 4-styrenesulfonate) (PSS), and poly(diallyldimethylammonium chloride) (PDADMAC) were mixed in the presence of excess of salt, thereby preventing complexation. Immersing a thin film of this mixture into a low-salinity bath induces complexation and consequently the precipitation of a solid PEC-based membrane. This approach leads to asymmetric nanofiltration membranes, with thin dense top layers and porous, macrovoid-free support layers. While the PSS molecular weight and the total polymer concentrations of the casting mixture did not significantly affect the membrane structure, they did affect the film formation process, the resulting mechanical stability of the films, and the membrane separation properties. The salt concentration of the coagulation bath has a large effect on membrane structure and allows for control over the thickness of the separation layer. The nanofiltration membranes prepared by APS have a low molecular weight cutoff (<300 Da), a high MgSO4 retention (∼80%), and good stability even at high pressures (10 bar). PE complexation induced APS is a simple and sustainable way to prepare membranes where membrane structure and performance can be tuned with molecular weight, polymer concentration, and ionic strength.

Abstract: Electrolytes featuring negatively charged polymers, such as nonaqueous polyelectrolyte solutions and polymerized ionic liquids, are currently under investigation as potential high cation transferen...

Abstract: Strongly interacting polyelectrolyte complexes (PECs) are known to form solid precipitates that can transform into liquid droplets upon the addition of salt to break intrinsic ionic associations. H...

Abstract: The interaction in aqueous solutions of surfactants with amphiphilic polymers can be more complex than the surfactant interactions with homopolymers. Interactions between the common ionic surfactant sodium dodecyl sulfate (SDS) and nonionic amphiphilic polymers of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) type have been probed utilizing a variety of experimental techniques. The polymer amphiphiles studied here are Pluronic F127 (EO100PO65EO100) and Pluronic P123 (EO19PO69EO19), having the same length PPO block but different length PEO blocks and, accordingly, very different critical micellization concentrations (CMC). With increasing surfactant concentration in aqueous solutions of fixed polymer content, SDS interacts with unassociated PEO-PPO-PEO molecules to first form SDS-rich SDS/Pluronic assemblies and then free SDS micelles. SDS interacts with micellized PEO-PPO-PEO to form Pluronic-rich SDS/Pluronic assemblies, which upon further increase in surfactant concentration, break down and transition into SDS-rich SDS/Pluronic assemblies, followed by free SDS micelle formation. The SDS-rich SDS/Pluronic assemblies exhibit polyelectrolyte characteristics. The interactions and mode of association between nonionic macromolecular amphiphiles and short-chain ionic amphiphiles are affected by the polymer hydrophobicity and its concentration in the aqueous solution. For example, SDS binds to Pluronic F127 micelles at much lower concentrations (~0.01 mM) when compared to Pluronic P123 micelles (~1 mM). The critical association concentration (CAC) values of SDS in aqueous PEO-PPO-PEO solutions are much lower than CAC in aqueous PEO homopolymer solutions.

Abstract: The versatility of polyelectrolyte multilayer (PEM) coatings is very promising for their use as separation layers in nanofiltration applications. These membranes can for example be suited for the r...

Abstract: The spontaneous association of oppositely charged polyelectrolytes is an example of liquid–liquid phase separation. The resulting hydrated polyelectrolyte complexes or coacervates, both termed “PEC...

Abstract: Many marine organisms have developed adhesives that are able to bond under water, overcoming the challenges associated with wet adhesion. A key element in the processing of several natural underwater glues is complex coacervation, a liquid-liquid phase separation driven by complexation of oppositely charged macromolecules. Inspired by these examples, the development of a fully synthetic complex coacervate-based adhesive is reported with an in situ setting mechanism, which can be triggered by a change in temperature and/or a change in ionic strength. The adhesive consists of a matrix of oppositely charged polyelectrolytes that are modified with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) grafts. The adhesive, which initially starts out as a fluid complex coacervate with limited adhesion at room temperature and high ionic strength, transitions into a viscoelastic solid upon an increase in temperature and/or a decrease in the salt concentration of the environment. Consequently, the thermoresponsive chains self-associate into hydrophobic domains and/or the polyelectrolyte matrix contracts, without inducing any macroscopic shrinking. The presence of PNIPAM favors energy dissipation by softening the material and by allowing crack blunting. The high work of adhesion, the gelation kinetics, and the easy tunability of the system make it a potential candidate for soft tissue adhesion in physiological environments.

Abstract: General features of rheological properties and structural peculiarities of polyelectrolyte polysaccharide-gelatin complexes were discussed in this paper. Experimental results were obtained for typical complexes, such as -carrageenan-gelatin, chitosan-gelatin and sodium alginate-gelatin complexes. A rheological method allows us to examine the physical state of a complex in aqueous phase and the kinetics of the sol-gel transition and temperature dependences of properties as a result of structural changes. The storage modulus below the gelation temperature is constant, which is a reflection of the solid-like state of a material. The gels of these complexes are usually viscoplastic media. The quantitative values of the rheological parameters depend on the ratio of the components in the complexes. The formation of the structure as a result of strong interactions of the components in the complexes was confirmed by UV and FTIR data and SEM analysis. Interaction with polysaccharides causes a change in the secondary structure of gelatin, i.e., the content of triple helices in an -chain increases. The joint analysis of the structural and rheological characteristics suggests that the formation of additional junctions in the complex gel network results in increases in elasticity and hardening compared with those of the native gelatin.