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Advances in Polyelectrolyte Complexes

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Applications".

Deadline for manuscript submissions: closed (15 May 2023) | Viewed by 19685

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Assoc. Prof. Dr. Christophe Schatz

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Guest Editor

Laboratoire de chimie des Polymères Organiques (LCPO) – CNRS, University of Bordeaux, Bordeaux Polytechnic Institute, UMR 5629, F-33600 Pessac, France
Interests: macromolecular assemblies in solution and at surface; polyelectrolyte complexation; complex coacervation; block copolymers self-assembly; out-of-equilibirum systems; chemistry and physicochemistry of polysaccharides; drug and gene delivery

Dr. Jean Paul Chapel

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Guest Editor

Centre de Recherche Paul Pascal (CRPP), UMR CNRS 5031, University of Bordeaux, F-33600 Pessac, France
Interests: soft matter physical-chemistry; colloids and macromolecules; self-assembly; out-of-equilibrium systems; polyelectrolytes; coacervates; functional surfaces and interface; organic thin films; glass transition

Special Issue Information

Dear Colleagues,

In 2020, the science of polyelectrolyte complexes (PECs) remains a lively area of research with a considerable impact on many other technological and scientifc fields, as shown, for example, by the current craze for complex coacervates in the field of synthetic biology and minimal cells. The fact that polyelectrolytes are now present in so many applications may explain this ever-growing interest in PECs. It is also worth pointing out that several key aspects of PECs are not yet fully explained, such as the exact mechanism ruling the interaction between two oppositely charged PEs, the influence of the nature and sequence of the charged units and counter-ions, the nature of added salts on interaction strength, but also the static and dynamic properties of complex coacervates, and other cutting-edge properties such as those found in stimuli-responsive systems. Therefore, fundamental research, modeling, and numerical simulations of complexation are more than ever necessary to deepen our know-how on PECs in order to take advantage of their endless properties. This Special Issue of Polymers aims at highlighting some of the recent advances made on PECs in different scientific fileds in order to put forward the concepts and properties shared by the various forms of complexes found in the literature, ranging from biological coacervates to synthetic complexes in solution, in bulk or at interface.

Assoc. Prof. Dr. Christophe Schatz
Dr. Jean Paul Chapel
Guest Editors

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Keywords

polyelectrolyte complexes
complex coacervation
biological polyelectrolytes
poly(ionic liquids)
conjugated polyelectrolytes
stimuli-responsive polyelectrolytes
structural and dynamics studies of polyelectrolyte complexes
modelling and simulations of polyelectrolyte complexes
complexation thermodynamics and kinetics
polyelectrolyte complexes at interface

Published Papers (9 papers)

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Research

19 pages, 3806 KiB

Open AccessArticle

Dilution-Induced Deposition of Concentrated Binary Mixtures of Cationic Polysaccharides and Surfactants

by Laura Fernández-Peña, Eduardo Guzmán, Teresa Oñate-Martínez, Coral Fernández-Pérez, Francisco Ortega, Ramón G. Rubio and Gustavo S. Luengo

Polymers 2023, 15(14), 3011; https://0-doi-org.brum.beds.ac.uk/10.3390/polym15143011 - 12 Jul 2023

Cited by 4 | Viewed by 1111

Abstract

This work investigates the effect of dilution on the phase separation process of binary charged polysaccharide–surfactant mixtures formed by two cationic polysaccharides and up to four surfactants of different nature (anionic, zwitterionic, and neutral), as well as the potential impact of dilution-induced phase separation on the formation of conditioning deposits on charged surfaces, mimicking the negative charge and wettability of damaged hair fibers. The results obtained showed that the dilution behavior of model washing formulations (concentrated polysaccharide–surfactant mixtures) cannot be described in terms of a classical complex precipitation framework, as phase separation phenomena occur even when the aggregates are far from the equilibrium phase separation composition. Therefore, dilution-enhanced deposition cannot be predicted in terms of the worsening of colloidal stability due to the charge neutralization phenomena, as common phase separation and, hence, enhanced deposition occurs even for highly charged complexes. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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19 pages, 10373 KiB

Open AccessArticle

Molecular Organization in Exponentially Growing Multilayer Thin Films Assembled with Polyelectrolytes and Clay

by Biswa P. Das and Marina Tsianou

Polymers 2022, 14(20), 4333; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14204333 - 14 Oct 2022

Cited by 1 | Viewed by 1410

Abstract

Multilayer thin film assembly by the layer-by-layer (LbL) technique offers an inexpensive and versatile route for the synthesis of functional nanomaterials. In the case of polymer-clay systems, however, the technique faces the challenges of low clay loading and lack of tunability of the film characteristics. This is addressed in the present work that achieves exponential growth in clay-containing polyelectrolyte films having high clay loading and tailored properties. Our approach involves the incorporation of a weak polyelectrolyte and a clay with relatively high charge density and small particle size. The system of investigation comprises poly(diallyldimethylammonium chloride) (PDDA) as the polycation and laponite clay and poly(acrylic acid) (PAA) or poly(sodium-4-styrene sulfonate) (PSS) as polyanions that are used alternately to create multilayers. Successful high clay loading and exponential growth were achieved by two different approaches of polyanion incorporation in the multilayers. A progressive increase in the degree of ionization of PAA was shown to contribute to the exponential growth. Our findings also include novel pathways to manipulate thickness, surface topography, and clay content. The strategy presented here can lead to novel approaches to fabricate tailor-made nanomaterials for distinct applications. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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15 pages, 4386 KiB

Open AccessArticle

Polyelectrolyte Chondroitin Sulfate Microgels as a Carrier Material for Rosmarinic Acid and Their Antioxidant Ability

by Mehtap Sahiner, Selin S. Suner, Aynur S. Yilmaz and Nurettin Sahiner

Polymers 2022, 14(20), 4324; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14204324 - 14 Oct 2022

Cited by 3 | Viewed by 1488

Abstract

Polyelectrolyte microgels derived from natural sources such as chondroitin sulfate (CS) possess considerable interest as therapeutic carriers because of their ionic nature and controllable degradation capability in line with the extent of the used crosslinker for long-term drug delivery applications. In this study, chemically crosslinked CS microgels were synthesized in a single step and treated with an ammonia solution to attain polyelectrolyte CS⁻[NH₄]⁺ microgels via a cation exchange reaction. The spherical and non-porous CS microgels were injectable and in the size range of a few hundred nanometers to tens of micrometers. The average size distribution of the CS microgels and their polyelectrolyte forms were not significantly affected by medium pH. It was determined that the −34 ± 4 mV zeta potential of the CS microgels was changed to −23 ± 3 mV for CS⁻ [NH₄]⁺ microgels with pH 7 medium. No important toxicity was determined on L929 fibroblast cells, with 76 ± 1% viability in the presence of 1000 μg/mL concentration of CS⁻[NH₄]⁺ microgels. Furthermore, these microgels were used as a drug carrier material for rosmarinic acid (RA) active agent. The RA-loading capacity was about 2.5-fold increased for CS⁻[R]⁺ microgels with 32.4 ± 5.1 μg/mg RA loading, and 23% of the loaded RA was sustainably release for a long-term period within 150 h in comparison to CS microgels. Moreover, RA-loaded CS⁻[R]⁺ microgels exhibited great antioxidant activity, with 0.45 ± 0.02 μmol/g Trolox equivalent antioxidant capacity in comparison to no antioxidant properties for bare CS particles. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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22 pages, 5289 KiB

Open AccessArticle

Complexation in Aqueous Solution of a Hydrophobic Polyanion (PSSNa) Bearing Different Charge Densities with a Hydrophilic Polycation (PDADMAC)

by Nouha Jemili, Martin Fauquignon, Etienne Grau, Nicolas Fatin-Rouge, François Dole, Jean-Paul Chapel, Wafa Essafi and Christophe Schatz

Polymers 2022, 14(12), 2404; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14122404 - 14 Jun 2022

Cited by 5 | Viewed by 2185

Abstract

In this work the electrostatic complexation of two strong polyelectrolytes (PEs) was studied, the hydrophilic and positively charged poly (diallyldimethylammonium chloride) (PDADMAC) and the hydrophobic and negatively charged poly (styrene-co-sodium styrene sulfonate) (P(St-co-SSNa)), which was prepared at different sulfonation rates. The latter is known to adopt a pearl necklace conformation in solution for intermediate sulfonation rates, suggesting that a fraction of the P(St-co-SSNa) charges might be trapped in these hydrophobic domains; thus making them unavailable for complexation. The set of complementary techniques (DLS, zetametry, ITC, binding experiment with a cationic and metachromatic dye) used in this work highlighted that this was not the case and that all anionic charges of P(St-co-SSNa) were in fact available for complexation either with the polycationic PDADMAC or the monocationic o-toluidine blue dye. Only minor differences were observed between these techniques, consistently showing a complexation stoichiometry close to 1:1 at the charge equivalence for the different P(St-co-SSNa) compositions. A key result emphasizing that (i) the strength of the electrostatic interaction overcomes the hydrophobic effect responsible for pearl formation, and (ii) the efficiency of complexation does not depend significantly on differences in charge density between PDADMAC and P(St-co-SSNa), highlighting that PE chains can undergo conformational rearrangements favoring the juxtaposition of segments of opposite charge. Finally, these data have shown that the formation of colloidal PECs, such as PDADMAC and P(St-co-SSNa), occurs in two distinct steps with the formation of small primary complex particles (<50 nm) by pairing of opposite charges (exothermic step) followed by their aggregation within finite-size clusters (endothermic step). This observation is in agreement with the previously described mechanism of PEC particle formation from strongly interacting systems containing a hydrophobic PE. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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12 pages, 2350 KiB

Open AccessArticle

One-Step Encapsulation of Capsaicin into Chitosan–Oleic Acid Complex Particles: Evaluation of Encapsulation Ability and Stability

by Takashi Kuroiwa and Yoshiki Higuchi

Polymers 2022, 14(11), 2163; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14112163 - 26 May 2022

Cited by 5 | Viewed by 2099

Abstract

Capsaicin (CAP) demonstrates a potential for application in the food and pharmaceutical industries owing to its various attractive health benefits, including anti-cancer, anti-inflammatory, and antioxidant activities. However, the application of CAP is often limited by its low solubility in water, low bioavailability, and strong pungency. In this study, a simple one-step method for the stable encapsulation and dispersion of CAP in aqueous media was developed using polyelectrolyte complex particles formed by chitosan (CHI) and oleic acid (OA). Homogeneous particles with mean diameters below 1 μm were successfully prepared via spontaneous molecular complexation by mixing an aqueous solution of CHI with an ethanolic solution of OA and CAP. CAP was incorporated into the hydrophobic domains of the CHI–OA complex particles through hydrophobic interactions between the alkyl chains of OA and CAP. The factors affecting CAP encapsulation were investigated, and a maximum encapsulation yield of approximately 100% was obtained. The CHI–OA–CAP complex particles could be stored for more than 3 months at room temperature (22–26 °C) without resulting in macroscopic phase separation or degradation of CAP. We believe that our findings provide a useful alternative encapsulation technique for CAP and contribute to expanding its practical application. Full article

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14 pages, 2996 KiB

Open AccessArticle

Synthetic Sulfated Polymers Control Amyloid Aggregation of Ovine Prion Protein and Decrease Its Toxicity

by Pavel Semenyuk, Diana Evstafyeva, Vladimir Izumrudov and Vladimir Muronetz

Polymers 2022, 14(7), 1478; https://0-doi-org.brum.beds.ac.uk/10.3390/polym14071478 - 05 Apr 2022

Cited by 2 | Viewed by 1753

Abstract

Amyloid aggregation, including aggregation and propagation of prion protein, is a key factor in numerous human diseases, so-called amyloidosis, with a very poor ability for treatment or prevention. The present work describes the effect of sulfated or sulfonated polymers (sodium dextran sulfate, polystyrene sulfonate, polyanethole sulfonate, and polyvinyl sulfate) on different stages of amyloidogenic conversion and aggregation of the prion protein, which is associated with prionopathies in humans and animals. All tested polymers turned out to induce amyloid conversion of the ovine prion protein. As suggested from molecular dynamics simulations, this effect probably arises from destabilization of the native prion protein structure by the polymers. Short polymers enhanced its further aggregation, whereas addition of high-molecular poly(styrene sulfonate) inhibited amyloid fibrils formation. According to the seeding experiments, the protein–polymer complexes formed after incubation with poly(styrene sulfonate) exhibited significantly lower amyloidogenic capacity compared with the control fibrils of the free prion protein. The cytotoxicity of soluble oligomers was completely inhibited by treatment with poly(styrene sulfonate). To summarize, sulfonated polymers are a promising platform for the formulation of a new class of anti-prion and anti-amyloidosis therapeutics. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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15 pages, 1390 KiB

Open AccessArticle

Interfacial Behavior of Solid- and Liquid-like Polyelectrolyte Complexes as a Function of Charge Stoichiometry

by Hongwei Li, Martin Fauquignon, Marie Haddou, Christophe Schatz and Jean-Paul Chapel

Polymers 2021, 13(21), 3848; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13213848 - 07 Nov 2021

Cited by 11 | Viewed by 2420

Abstract

We systematically investigate in this work the surface activity of polyelectrolyte complex (PECs) suspensions as a function of the molar charge ratio Z (= [-]/[+]) from two model systems: the weakly and strongly interacting poly (diallyldimethylammonium chloride)/poly (acrylic acid sodium salt) (PDADMAC/PANa) and poly (diallyldimethylammonium chloride)/poly (sodium 4- styrenesulfonate) (PDADMAC/PSSNa) pairs, respectively. For both systems, the PEC surface tension decreases as the system approaches charge stoichiometry (Z = 1) whenever the complexation occurs in the presence of excess PDADMAC (Z < 1) or excess polyanion (Z > 1) consistent with an increased level of charge neutralization of PEs forming increasingly hydrophobic and neutral surface-active species. The behavior at stoichiometry (Z = 1) is also particularly informative about the physical nature of the complexes. The PDADMAC/PANa system undergoes a liquid–liquid phase transition through the formation of coacervate microdroplets in equilibrium with macroions remaining in solution. In the PDADMAC/PSSNa system, the surface tension of the supernatant was close to that of pure water, suggesting that the PSSNa-based complexes have completely sedimented, consistent with a complete liquid–solid phase separation of an out-of-equilibrium system. Besides, the high sensitivity of surface tension measurements, which can detect the presence of trace amounts of aggregates and other precursors in the supernatant, allows for very accurate determination of the exact charge stoichiometry of the complexes. Finally, the very low water/water interfacial tension that develops between the dilute phase and the denser coacervate phase in the PDADAMAC/PANa system was measured using the generalized Young–Laplace method to complete the full characterization of both systems. The overall study showed that simple surface tension measurements can be a very sensitive tool to characterize, discriminate, and better understand the formation mechanism of the different structures encountered during the formation of PECs. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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13 pages, 1538 KiB

Open AccessArticle

Preparation of Poly(acrylate)/Poly(diallyldimethylammonium) Coacervates without Small Counterions and Their Phase Behavior upon Salt Addition towards Poly-Ions Segregation

by Marcos Vinícius Aquino Queirós and Watson Loh

Polymers 2021, 13(14), 2259; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13142259 - 09 Jul 2021

Cited by 4 | Viewed by 2000

Abstract

In this work, we report the phase behavior of polyelectrolyte complex coacervates (PECs) of poly(acrylate) (PA⁻) and poly(diallyldimethylammonium) (PDADMA⁺) in the presence of inorganic salts. Titrations of the polyelectrolytes in their acidic and alkaline forms were performed to obtain the coacervates in the absence of their small counterions. This approach was previously applied to the preparation of polymer–surfactant complexes, and we demonstrate that it also succeeded in producing complexes free of small counterions with a low extent of Hofmann elimination. For phase behavior studies, two different molar masses of poly(acrylate) and two different salts were employed over a wide concentration range. It was possible to define the regions at which associative and segregative phase separation take place. The latter one was exploited in more details because the segregation phenomenon in mixtures of oppositely charged polyelectrolytes is scarcely reported. Phase composition analyses showed that there is a strong segregation for both PA⁻ and PDADMA⁺, who are accompanied by their small counterions. These results demonstrate that the occurrence of poly-ion segregation in these mixtures depends on the anion involved: in this case, it was observed with NaCl, but not with Na₂SO₄. Full article

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18 pages, 3406 KiB

Open AccessArticle

Deciphering the Role of π-Interactions in Polyelectrolyte Complexes Using Rationally Designed Peptides

by Sara Tabandeh, Cristina Elisabeth Lemus and Lorraine Leon

Polymers 2021, 13(13), 2074; https://0-doi-org.brum.beds.ac.uk/10.3390/polym13132074 - 24 Jun 2021

Cited by 6 | Viewed by 3756

Abstract

Electrostatic interactions, and specifically π-interactions play a significant role in the liquid-liquid phase separation of proteins and formation of membraneless organelles/or biological condensates. Sequence patterning of peptides allows creating protein-like structures and controlling the chemistry and interactions of the mimetic molecules. A library of oppositely charged polypeptides was designed and synthesized to investigate the role of π-interactions on phase separation and secondary structures of polyelectrolyte complexes. Phenylalanine was chosen as the π-containing residue and was used together with lysine or glutamic acid in the design of positively or negatively charged sequences. The effect of charge density and also the substitution of fluorine on the phenylalanine ring, known to disrupt π-interactions, were investigated. Characterization analysis using MALDI-TOF mass spectroscopy, H NMR, and circular dichroism (CD) confirmed the molecular structure and chiral pattern of peptide sequences. Despite an alternating sequence of chirality previously shown to promote liquid-liquid phase separation, complexes appeared as solid precipitates, suggesting strong interactions between the sequence pairs. The secondary structures of sequence pairs showed the formation of hydrogen-bonded structures with a β-sheet signal in FTIR spectroscopy. The presence of fluorine decreased hydrogen bonding due to its inhibitory effect on π-interactions. π-interactions resulted in enhanced stability of complexes against salt, and higher critical salt concentrations for complexes with more π-containing amino acids. Furthermore, UV-vis spectroscopy showed that sequences containing π-interactions and increased charge density encapsulated a small charged molecule with π-bonds with high efficiency. These findings highlight the interplay between ionic, hydrophobic, hydrogen bonding, and π-interactions in polyelectrolyte complex formation and enhance our understanding of phase separation phenomena in protein-like structures. Full article

(This article belongs to the Special Issue Advances in Polyelectrolyte Complexes)

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