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Advances in Polyelectrolytes and Polyelectrolyte Complexes

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

Deadline for manuscript submissions: 25 July 2024 | Viewed by 4209

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Special Issue Editors

Dr. Paulina Mocchiutti

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Guest Editor

1. Instituto de Tecnología Celulósica, Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santa Fe, Argentina
2. Consejo Nacional de Investigaciones Científicas y Técnicas, Santa Fe, Argentina
Interests: biobased materials; packaging films; controlled drug delivery; hydrogels; polysaccharides; mechanical properties; polyelectrolyte complexes; paper strength additives; cellulose nanofibrillar

Prof. Dr. Anupama Sharma

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Guest Editor

SSB University Institute of Chemical Engineering and Technology, Panjab University, Chandigarh 160014, India
Interests: biomass valorization; cellulose nanofibers; biopolymers for wastewater remediation; polymer bionanocomposites; cellulose- and hemicellulose-based hydrogels

Dr. Norma E. Marcovich

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Guest Editor

1. Departamento de Ingeniería Química y en Alimentos (DIQyA), Facultad de Ingeniería, Universidad Nacional de Mar del Plata, Mar del Plata, Argentina
2. Instituto de Investigaciones en Ciencia y Tecnología de Materiales (INTEMA), Consejo Nacional de Investigaciones Científicas y Técnicas, Mar del Plata, Argentina
Interests: biobased polymers; natural polymers; functional properties; vitrimers; food packaging; magnetic nanocomposites

Special Issue Information

Dear Colleagues,

Natural and synthetic polyelectrolytes have gained great interest in the last years for different applications. Polyelectrolyte complexes (PECs) are micro-/nanostructured units with exceptional properties obtained via the polymeric interaction between cationic and anionic polyelectrolytes. The properties are affected by the conditions of the liquid medium, the order of addition of the polyelectrolytes, the mass ratio, and the polyelectrolyte concentration, among others.

This Special Issue aims to collect research papers, communications, and review articles with original contributions to the development of novel materials prepared using polyelectrolytes or polyelectrolyte complexes. Information about the relationship between the chemical structure of the polyelectrolytes and the characteristics of the PECs obtained from the morphology, thermal, optical, and/or mechanical properties of the materials based on PECs is relevant. The Special Issue covers, among other topics, polyelectrolyte and polyelectrolyte complexes in:

Multilayers.
Drug delivery.
Wound healing and tissue engineering.
Packaging films.
Paper additives and coatings.
Membranes and gels.
Bioadhesives.

Dr. Paulina Mocchiutti
Prof. Dr. Anupama Sharma
Dr. Norma E. Marcovich
Guest Editors

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

polyelectrolyte complex characterization
mechanical properties
thermal properties
controlled drug delivery
hydrogels
packaging films
paper additives
coating

Published Papers (5 papers)

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Research

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17 pages, 4598 KiB

Open AccessArticle

Investigation of Silk Fibroin/Poly(Acrylic Acid) Interactions in Aqueous Solution

by Jelena Škrbić, Ljiljana Spasojević, Altynay Sharipova, Saule Aidarova, Alpamys Babayev, Raziya Sarsembekova, Ljiljana Popović, Sandra Bučko, Jelena Milinković Budinčić, Jadranka Fraj, Lidija Petrović and Jaroslav Katona

Polymers 2024, 16(7), 936; https://doi.org/10.3390/polym16070936 - 29 Mar 2024

Viewed by 540

Abstract

Silk fibroin (SF) is a protein with many outstanding properties (superior biocompatibility, mechanical strength, etc.) and is often used in many advanced applications (epidermal sensors, tissue engineering, etc.). The properties of SF-based biomaterials may additionally be tuned by SF interactions with other (bio)polymers. Being a weak amphoteric polyelectrolyte, SF may form polyelectrolyte complexes (PECs) with other polyelectrolytes of opposite charge, such as poly(acrylic acid) (PAA). PAA is a widely used, biocompatible, synthetic polyanion. Here, we investigate PEC formation between SF and PAA of two different molecular weights (MWs), low and high, using various techniques (turbidimetry, zeta potential measurements, capillary viscometry, and tensiometry). The colloidal properties of SF isolated from Bombyx mori and of PAAs (MW, overlap concentration, the influence of pH on zeta potential, adsorption at air/water interface) were determined to identify conditions for the SF-PAA electrostatic interaction. It was shown that SF-PAA PEC formation takes place at different SF:PAA ratios, at pH 3, for both high and low MW PAA. SF-PAA PEC’s properties (phase separation, charge, and surface activity) are influenced by the SF:PAA mass ratio and/or the MW of PAA. The findings on the interactions contribute to the future development of SP-PAA PEC-based films and bioadhesives with tailored properties. Full article

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

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17 pages, 11586 KiB

Open AccessArticle

Humic Polyelectrolytes Facilitate Rapid Microwave Synthesis of Silver Nanoparticles Suitable for Wound-Healing Applications

by Yu Zhang, Konstantin S. Larionov, Simeng Zhang, Nikita A. Sobolev, Andrey I. Konstantinov, Dmitry S. Volkov, Evgeniya V. Suslova, Vladimir E. Chernov, Anton I. Poloskov, Ruslan I. Glushakov and Irina V. Perminova

Polymers 2024, 16(5), 587; https://doi.org/10.3390/polym16050587 - 21 Feb 2024

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Abstract

This article describes the one-pot microwave synthesis of silver nanoparticles (AgNPs) assisted with natural polyelectrolytes—humic substances (HS). The humic polyelectrolytes served both as chemical reductants for silver ions and as end-capping agents for AgNPs. Three commercially available sodium humates extracted from lignites and leonardite and one sodium fulvate isolated from natural brown water seeped through peat deposits were used in this study. The dynamics of the growth rate of AgNPs was characterised by UV–VIS spectroscopy by measuring the intensity of surface plasmon resonance at 420 nm. Transmission electron microscopy was used to characterise the size and morphology of AgNPs. Dynamic light scattering was used to determine size distributions of the synthesised AgNPs in the solutions. It was established that both conventional and microwave syntheses assisted with the coal humates produced small-size AgNPs in the range from 4 to 14 nm, with the maximum share of particles with sizes of (6 ± 2) nm by TEM estimates. The peat fulvate yielded much larger NPs with sizes from 10 to 50 nm by TEM estimates. DLS measurements revealed multimodal distributions of AgNPs stabilised with HS, which included both single NPs with the sizes from 5 to 15 nm, as well as their dominating aggregates with sizes from 20 to 200 nm and a smaller portion of extra-large aggregates up to 1000 nm. The given aggregates were loosely bound by humic polyelectrolyte, which prevented the coalescence of AgNPs into larger particles, as can be seen in the TEM images. The significant acceleration in the reaction time—a factor of 60 to 70—was achieved with the use of MW irradiation: from 240 min down to 210–240 s. The coal humate stabilised AgNPs showed antimicrobial properties in relation to S. aureus. A conclusion was made regarding the substantial advantages of microwave synthesis in the context of time and scaling up for the large-scale production of AgNP-HS preparations with antimicrobial properties suitable for external wound-healing applications. Full article

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

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Graphical abstract

15 pages, 39415 KiB

Open AccessArticle

A Novel Fractional Brownian Dynamics Method for Simulating the Dynamics of Confined Bottle-Brush Polymers in Viscoelastic Solution

by Shi Yu, Ruizhi Chu, Guoguang Wu and Xianliang Meng

Polymers 2024, 16(4), 524; https://doi.org/10.3390/polym16040524 - 15 Feb 2024

Viewed by 499

Abstract

In crowded fluids, polymer segments can exhibit anomalous subdiffusion due to the viscoelasticity of the surrounding environment. Previous single-particle tracking experiments revealed that such anomalous diffusion in complex fluids (e.g., in bacterial cytoplasm) can be described by fractional Brownian motion (fBm). To investigate how the viscoelastic media affects the diffusive behaviors of polymer segments without resolving single crowders, we developed a novel fractional Brownian dynamics method to simulate the dynamics of polymers under confinement. In this work, instead of using Gaussian random numbers (“white Gaussian noise”) to model the Brownian force as in the standard Brownian dynamics simulations, we introduce fractional Gaussian noise (fGn) in our homemade fractional Brownian dynamics simulation code to investigate the anomalous diffusion of polymer segments by using a simple “bottle-brush”-type polymer model. The experimental results of the velocity autocorrelation function and the exponent that characterizes the subdiffusion of the confined polymer segments can be reproduced by this simple polymer model in combination with fractional Gaussian noise (fGn), which mimics the viscoelastic media. Full article

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

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16 pages, 6765 KiB

Open AccessArticle

Ultrasensitive Detection of PSA Using Antibodies in Crowding Polyelectrolyte Multilayers on a Silicon Nanowire Field-Effect Transistor

by Galina V. Presnova, Denis E. Presnov, Mariya M. Ulyashova, Ilia I. Tsiniaikin, Artem S. Trifonov, Ekaterina V. Skorb, Vladimir A. Krupenin, Oleg V. Snigirev and Maya Yu. Rubtsova

Polymers 2024, 16(3), 332; https://doi.org/10.3390/polym16030332 - 25 Jan 2024

Viewed by 939

Abstract

Immunosensors based on field-effect transistors with nanowire channels (NWFETs) provide fast and real-time detection of a variety of biomarkers without the need for additional labels. The key feature of the developed immunosensor is the coating of silicon NWs with multilayers of polyelectrolytes (polyethylenimine (PEI) and polystyrene sulfonate (PSS)). By causing a macromolecular crowding effect, it ensures the “soft fixation” of the antibodies into the 3-D matrix of the oppositely charged layers. We investigated the interaction of prostate-specific antigen (PSA), a biomarker of prostate cancer, and antibodies adsorbed in the PEI and PSS matrix. In order to visualize the formation of immune complexes between polyelectrolyte layers using SEM and AFM techniques, we employed a second clone of antibodies labeled with gold nanoparticles. PSA was able to penetrate the matrix and concentrate close to the surface layer, which is crucial for its detection on the nanowires. Additionally, this provides the optimal orientation of the antibodies’ active centers for interacting with the antigen and improves their mobility. NWFETs were fabricated from SOI material using high-resolution e-beam lithography, thin film vacuum deposition, and reactive-ion etching processes. The immunosensor was characterized by a high sensitivity to pH (71 mV/pH) and an ultra-low limit of detection (LOD) of 0.04 fg/mL for PSA. The response of the immunosensor takes less than a minute, and the measurement is carried out in real time. This approach seems promising for further investigation of its applicability for early screening of prostate cancer and POC systems. Full article

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

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Review

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15 pages, 2833 KiB

Open AccessReview

Polyelectrolytes: From Seminal Works to the Influence of the Charge Sequence

by Nam-Kyung Lee, Min-Kyung Chae, Youngkyun Jung, Albert Johner and Jean-Francois Joanny

Polymers 2023, 15(23), 4593; https://doi.org/10.3390/polym15234593 - 30 Nov 2023

Viewed by 858

Abstract

We propose a selected tour of the physics of polyelectrolytes (PE) following the line initiated by de Gennes and coworkers in their seminal 1976 paper. The early works which used uniform charge distributions along the PE backbone achieved tremendous progress and set most milestones in the field. Recently, the focus has shifted to the role of the charge sequence. Revisited topics include PE complexation and polyampholytes (PA). We develop the example of a random PE in poor solvent forming pearl-necklace structures. It is shown that the pearls typically adopt very asymmetric mass and charge distributions. Individual sequences do not necessarily reflect the ensemble statistics and a rich variety of behaviors emerges (specially for PA). Pearl necklaces are dynamic structures and switch between various types of pearl-necklace structures, as described for both PE and PA. Full article

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

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