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Polymers
Special Issues
Polyelectrolytes and Interpolyelectrolyte Complexes
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Polyelectrolytes and Interpolyelectrolyte Complexes

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

Deadline for manuscript submissions: closed (15 September 2022) | Viewed by 14477

Special Issue Editor

Dr. Dmitry V. Pergushov

E-Mail Website
Guest Editor
Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, 119991 Moscow, Russia
Interests: polyelectrolytes; ionic (co)polymers; stimuli-sensitive (co)polymers; macromolecular (self-/co-)assembly; interpolyelectrolyte complexes; polyelectrolyte multilayers; applications of polyelectrolyte-based systems

Special Issue Information

Dear Colleagues,

Polyelectrolytes compose an important class of water-soluble polymers whose high functionality comes from the many ionic groups they bear. Natural polyelectrolytes like nucleic acids and proteins, as well as their assemblies, play a vital role in biological systems. Synthetically produced polyelectrolytes, which are nowadays very diverse in their composition, structure, and topology due to substantial progress in controlled polymerization techniques, are in demand because of their many applications—as flocculants, binders, coatings, rheology modifiers, etc. Even more functional and advanced macromolecular structures can be obtained when oppositely charged polyelectrolytes, either synthetic or natural, interact with each other. The products of this interaction, which is mainly electrostatic in its nature, are referred to as interpolyelectrolyte complexes, complex coacervates, or polyion complexes in the literature. Combining properties of their polymeric components, they at the same time possess features which make them unique self-organizing and adaptive macromolecular assemblies and already find (or hold promise for) application in many important fields such as materials engineering, medicine/biotechnology, ecology, etc., for example as polyelectrolyte multilayer coatings, interpolyelectrolyte complex binders and structure-forming agents, drug and non-viral gene carriers, etc.

This Special Issue is focused on recent advances in the physico-chemistry of polyelectrolytes and their assemblies in solution and at interfaces, with particular emphasis to stimuli-sensitive complex structures, their characterization, and (potential) applications. It aims at collecting papers considering such macromolecular systems both from a fundamental (including simulation/modeling) and an application-oriented point of view to outline emerging trends and main developments in this field of polymer science and related areas where ionic (co)polymers are exploited to impart functionality to already existing constructs or to create novel responsive (in the broadest sense of the word) systems.

Reviews, mini-reviews, and original research papers are welcome. There is particular interest in papers reporting yet unexplored (multi)functional systems based on ionic (co)polymers and approaches to their fabrication, characterization, and application.

Dr. Dmitry V. Pergushov
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • polyelectrolytes
  • ionic (co)polymers
  • macromolecular assembly
  • interpolyelectrolyte complexes
  • complex coacervates
  • polyion complexes
  • polyelectrolyte multilayers
  • applications of polyelectrolyte-based systems

Published Papers (5 papers)

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Research

16 pages, 2674 KiB  
Article
A Polyelectrolyte Colloidal Brush Based on Cellulose: Perspectives for Future Applications
by Michael A. Smirnov, Vitaly K. Vorobiov, Veronika S. Fedotova, Maria P. Sokolova, Natalya V. Bobrova, Nikolay N. Smirnov and Oleg V. Borisov
Polymers 2023, 15(23), 4526; https://doi.org/10.3390/polym15234526 - 25 Nov 2023
Viewed by 889
Abstract
This feature article is devoted to the evaluation of different techniques for producing colloidal polyelectrolyte brushes (CPEBs) based on cellulose nanofibers modified with grafted polyacrylates. The paper also reviews the potential applications of these CPEBs in designing electrode materials and as reinforcing additives. [...] Read more.
This feature article is devoted to the evaluation of different techniques for producing colloidal polyelectrolyte brushes (CPEBs) based on cellulose nanofibers modified with grafted polyacrylates. The paper also reviews the potential applications of these CPEBs in designing electrode materials and as reinforcing additives. Additionally, we discuss our own perspectives on investigating composites with CPEBs. Herein, polyacrylic acid (PAA) was grafted onto the surface of cellulose nanofibers (CNFs) employing a “grafting from” approach. The effect of the PAA shell on the morphological structure of a composite with polypyrrole (PPy) was investigated. The performance of as-obtained CNF-PAA/PPy as organic electrode material for supercapacitors was examined. Furthermore, this research highlights the ability of CNF-PAA filler to act as an additional crosslinker forming a physical sub-network due to the hydrogen bond interaction inside chemically crosslinked polyacrylamide (PAAm) hydrogels. The enhancement of the mechanical properties of the material with a concomitant decrease in its swelling ratio compared to a pristine PAAm hydrogel was observed. The findings were compared with the recent theoretical foundation pertaining to other similar materials. Full article
(This article belongs to the Special Issue Polyelectrolytes and Interpolyelectrolyte Complexes)
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18 pages, 4891 KiB  
Article
A Comparison of Interpolyelectrolyte Complexes (IPECs) Made from Anionic Block Copolymer Micelles and PDADMAC or q-Chitosan as Polycation
by Özge Azeri, Dennis Schönfeld, Bin Dai, Uwe Keiderling, Laurence Noirez and Michael Gradzielski
Polymers 2023, 15(9), 2204; https://doi.org/10.3390/polym15092204 - 06 May 2023
Viewed by 1324
Abstract
Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and [...] Read more.
Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and the degree of polymerisation in this block. Depending on the architecture of the hydrophobic part, they had a more or less pronounced tendency to form copolymer micelles in an aqueous solution. They were employed for the preparation of IPECs by mixing the copolymer aggregates with the polycations polydiallyldimethylammonium chloride (PDADMAC) or q-chit. The IPEC structure as a function of the composition was investigated by Static Light and Small Angle Neutron Scattering. For weakly-associated block copolymers (short alkyl chain), complexation with polycation led to the formation of globular complexes, while already existing micelles (long alkyl chain) grew further in mass. In general, aggregates became larger upon the addition of further polycation, but this growth was much more pronounced for PDADMAC compared to q-chit, thereby leading to the formation of clusters of aggregates. Accordingly, the structure of such IPECs with a hydrophobic block depended largely on the type of complexing polyelectrolyte, which allowed for controlling the structural organisation via the molecular architecture of the two oppositely charged polyelectrolytes. Full article
(This article belongs to the Special Issue Polyelectrolytes and Interpolyelectrolyte Complexes)
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12 pages, 6117 KiB  
Article
Thin Porous Poly(ionic liquid) Coatings for Enhanced Headspace Solid Phase Microextraction
by David J. S. Patinha, Hong Wang, Jiayin Yuan, Sílvia M. Rocha, Armando J. D. Silvestre and Isabel M. Marrucho
Polymers 2020, 12(9), 1909; https://doi.org/10.3390/polym12091909 - 24 Aug 2020
Cited by 9 | Viewed by 2973
Abstract
In this contribution, thin poly(ionic liquid) (PIL) coatings with a well-defined pore structure built up from interpolyelectrolyte complexation between a PIL and poly(acrylic acid) (PAA) were successfully used for enhanced solid phase microextraction (SPME). The introduction of porosity with tunable polarity through the [...] Read more.
In this contribution, thin poly(ionic liquid) (PIL) coatings with a well-defined pore structure built up from interpolyelectrolyte complexation between a PIL and poly(acrylic acid) (PAA) were successfully used for enhanced solid phase microextraction (SPME). The introduction of porosity with tunable polarity through the highly versatile PIL chemistry clearly boosts the potential of SPME in the detection of compounds at rather low concentrations. This work will inspire researchers to further explore the potential of porous poly(ionic liquid) materials in sensing and separation applications. Full article
(This article belongs to the Special Issue Polyelectrolytes and Interpolyelectrolyte Complexes)
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19 pages, 3329 KiB  
Article
Rational Design of Amphiphilic Diblock Copolymer/MWCNT Surface Modifiers and Their Application for Direct Electrochemical Sensing of DNA
by Larisa V. Sigolaeva, Tatiana V. Bulko, Apollinariya Yu. Konyakhina, Alexey V. Kuzikov, Rami A. Masamrekh, Johannes B. Max, Moritz Köhler, Felix H. Schacher, Dmitry V. Pergushov and Victoria V. Shumyantseva
Polymers 2020, 12(7), 1514; https://doi.org/10.3390/polym12071514 - 08 Jul 2020
Cited by 11 | Viewed by 3551
Abstract
We demonstrate the application of amphiphilic ionic poly(n-butylmethacrylate)-block- poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers (PnBMA40-b-PDMAEMA40, PnBMA40-b-PDMAEMA120, PnBMA70-b-PDMAEMA120) [...] Read more.
We demonstrate the application of amphiphilic ionic poly(n-butylmethacrylate)-block- poly(2-(dimethylamino)ethyl methacrylate) diblock copolymers (PnBMA40-b-PDMAEMA40, PnBMA40-b-PDMAEMA120, PnBMA70-b-PDMAEMA120) for dispersing multiwalled carbon nanotubes (MWCNTs) in aqueous media, a subsequent efficient surface modification of screen-printed electrodes (SPEs), and the application of the modified SPEs for DNA electrochemistry. Stable and fine aqueous dispersions of MWCNTs were obtained with PnBMAx-b-PDMAEMAy diblock copolymers, regardless of the structure of the copolymer and the amount of MWCNTs in the dispersions. The effect of the diblock copolymer structure was important when the dispersions of MWCNTs were deposited as modifying layers on surfaces of SPEs, resulting in considerable increases of the electroactive surface areas and great acceleration of the electron transfer rate. The SPE/(PnBMAx-b-PDMAEMAy + MWCNT) constructs were further exploited for direct electrochemical oxidation of the guanine (G) and adenine (A) residues in a model salmon sperm double-stranded DNA (dsDNA). Two well-defined irreversible oxidation peaks were observed at about +600 and +900 mV, corresponding to the electrochemical oxidation of G and A residues, respectively. A multi-parametric optimization of dsDNA electrochemistry enables one to get the limits of detection (LOD) as low as 5 μg/mL (0.25 μM) and 1 μg/mL (0.05 μM) for G and A residues, respectively. The achieved sensitivity of DNA assay enables quantification of the A and G residues of dsDNA in the presence of human serum and DNA in isolated human leukocytes. Full article
(This article belongs to the Special Issue Polyelectrolytes and Interpolyelectrolyte Complexes)
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14 pages, 3598 KiB  
Article
Polyelectrolyte Polysaccharide–Gelatin Complexes: Rheology and Structure
by Svetlana R. Derkach, Yuliya A. Kuchina, Daria S. Kolotova and Nikolay G. Voron’ko
Polymers 2020, 12(2), 266; https://doi.org/10.3390/polym12020266 - 26 Jan 2020
Cited by 36 | Viewed by 4927
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 κ-carrageenan–gelatin, chitosan–gelatin and sodium alginate–gelatin complexes. A rheological method allows us to examine the physical state of [...] Read more.
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 κ-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 α-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. Full article
(This article belongs to the Special Issue Polyelectrolytes and Interpolyelectrolyte Complexes)
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