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Keywords = branched polyelectrolyte complex

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23 pages, 9067 KB  
Article
Anionic Hyperbranched Amphiphilic Polyelectrolytes as Nanocarriers for Antimicrobial Proteins and Peptides
by Anastasia Balafouti, Aleksander Forys, Barbara Trzebicka, Angelica Maria Gerardos and Stergios Pispas
Materials 2023, 16(24), 7702; https://doi.org/10.3390/ma16247702 - 18 Dec 2023
Cited by 1 | Viewed by 2125
Abstract
This manuscript presents the synthesis of hyperbranched amphiphilic poly (lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), H-P(LMA-co-tBMA-co-MAA) copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization of tBMA and LMA, and their post-polymerization modification to anionic amphiphilic polyelectrolytes. The focus is on investigating whether the combination [...] Read more.
This manuscript presents the synthesis of hyperbranched amphiphilic poly (lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), H-P(LMA-co-tBMA-co-MAA) copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization of tBMA and LMA, and their post-polymerization modification to anionic amphiphilic polyelectrolytes. The focus is on investigating whether the combination of the hydrophobic characters of LMA and tBMA segments, as well as the polyelectrolyte and hydrophilic properties of MAA segments, both distributed within a unique hyperbranched polymer chain topology, would result in intriguing, branched copolymers with the potential to be applied in nanomedicine. Therefore, we studied the self-assembly behavior of these copolymers in aqueous media, as well as their ability to form complexes with cationic proteins, namely lysozyme (LYZ) and polymyxin (PMX). Various physicochemical characterization techniques, including size exclusion chromatography (SEC) and proton nuclear magnetic resonance (1H-NMR), verified the molecular characteristics of these well-defined copolymers, whereas light scattering and fluorescence spectroscopy techniques revealed promising nanoparticle (NP) self- and co-assembly properties of the copolymers in aqueous media. Full article
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19 pages, 9026 KB  
Article
Hyperbranched Copolymers of Methacrylic Acid and Lauryl Methacrylate H-P(MAA-co-LMA): Synthetic Aspects and Interactions with Biorelevant Compounds
by Anastasia Balafouti and Stergios Pispas
Pharmaceutics 2023, 15(4), 1198; https://doi.org/10.3390/pharmaceutics15041198 - 9 Apr 2023
Cited by 11 | Viewed by 4112
Abstract
The synthesis of novel copolymers using one-step reversible addition-fragmentation chain transfer (RAFT) copolymerization of biocompatible methacrylic acid (MAA), lauryl methacrylate (LMA), and difunctional ethylene glycol dimethacrylate (EGDMA) as a branching agent is reported. The obtained amphiphilic hyperbranched H-P(MAA-co-LMA) copolymers are molecularly characterized by [...] Read more.
The synthesis of novel copolymers using one-step reversible addition-fragmentation chain transfer (RAFT) copolymerization of biocompatible methacrylic acid (MAA), lauryl methacrylate (LMA), and difunctional ethylene glycol dimethacrylate (EGDMA) as a branching agent is reported. The obtained amphiphilic hyperbranched H-P(MAA-co-LMA) copolymers are molecularly characterized by size exclusion chromatography (SEC), FTIR, and 1H-NMR spectroscopy, and subsequently investigated in terms of their self-assembly behavior in aqueous media. The formation of nanoaggregates of varying size, mass, and homogeneity, depending on the copolymer composition and solution conditions such as concentration or pH variation, is demonstrated by light scattering and spectroscopic techniques. Furthermore, drug encapsulation properties are studied by incorporating the low bioavailability drug, curcumin, in the nano-aggregate hydrophobic domains, which can also act as a bioimaging agent. The interaction of polyelectrolyte MAA units with model proteins is described to examine protein complexation capacity relevant to enzyme immobilization strategies, as well as explore copolymer self-assembly in simulated physiological media. The results confirm that these copolymer nanosystems could provide competent biocarriers for imaging and drug or protein delivery/enzyme immobilization applications. Full article
(This article belongs to the Special Issue Self-Assembled Amphiphilic Copolymers in Drug Delivery)
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20 pages, 3567 KB  
Article
Nanodispersions of Polyelectrolytes Based on Humic Substances: Isolation, Physico-Chemical Characterization and Evaluation of Biological Activity
by Elena V. Uspenskaya, Anton V. Syroeshkin, Tatiana V. Pleteneva, Ilaha V. Kazimova, Tatiana V. Grebennikova, Irina T. Fedyakina, Varvara V. Lebedeva, Oleg E. Latyshev, Olesia V. Eliseeva, Viktor F. Larichev, Timur M. Garaev, Tatiana V. Maximova, Mariya A. Morozova and Pham My Hanh
Pharmaceutics 2021, 13(11), 1954; https://doi.org/10.3390/pharmaceutics13111954 - 18 Nov 2021
Cited by 12 | Viewed by 4644
Abstract
Natural polyelectrolytes, including in the form of complexes with colloidal particles, are increasingly used in pharmacy due to the possibility of regulated attachment of medicinal substances and their targeted delivery to the target organ. However, the formation, stability, and molecular-mass characteristics of polyelectrolyte [...] Read more.
Natural polyelectrolytes, including in the form of complexes with colloidal particles, are increasingly used in pharmacy due to the possibility of regulated attachment of medicinal substances and their targeted delivery to the target organ. However, the formation, stability, and molecular-mass characteristics of polyelectrolyte nanodispersions (ND) vary depending on the nature and composition of the medium of their origin. This is due to the lack of standardized approaches to quality control and regulatory documentation for most natural ND. In this paper, we first introduced the isolation, followed by investigations into their physico-chemical properties and bioactivity. Using the dried droplet method, we were able to detect the “coffee ring effect”. Fractographic studies of the surface structure of EHA and FA dried samples using SEM showed its heterogeneity and the presence of submicron particles encapsulated in the internal molecular cavities of polyelectrolyte. FTIR spectroscopy revealed the ND chemical structure of benzo-α-pyron and benzo-γ-pyron, consisting of nanoparticles and a branched frame part. The main elements detected by X-ray fluorescence in humic substance extract and fulvic acid include Si, P, S, K, Ca, Mn, Fe, Cu, Zn, whereas Fe is in high concentrations. The UV-spectra and fluorescent radiation demonstrated the possibility of studying the effect of the fulvate chromone structure on its optical properties. It is shown that dilution of the initial solutions of polyelectrolytes 1:10 contributes to the detection of smaller nanoparticles and an increase in the absolute value of the negative ζ-potential as a factor of ND stability. A study of the EHS effect on the SARS-CoV-2 virus infectious titer in the Vero E6 cell showed the effective against virus both in the virucidal scheme (the SI is 11.90–22.43) and treatment/prevention scheme (the SI is 34.85–57.33). We assume that polyelectrolyte ND prevent the binding of the coronavirus spike glycoprotein to the receptor. Taking into account the results obtained, we expect that the developed approach can become unified for the standardization of the ND natural polyelectrolytes complex, which has great prospects for use in pharmacy and medicine as a drug with antiviral activity. Full article
(This article belongs to the Special Issue New Properties of Supramolecular Complexes and Drug Nanoparticles)
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13 pages, 5635 KB  
Article
A Branched Polyelectrolyte Complex Enables Efficient Flame Retardant and Excellent Robustness for Wood/Polymer Composites
by Yanping Huang, Shuai Zhang, He Chen, Chunxiang Ding, Yan Xuan, Mingzhu Pan and Changtong Mei
Polymers 2020, 12(11), 2438; https://doi.org/10.3390/polym12112438 - 22 Oct 2020
Cited by 17 | Viewed by 3670
Abstract
Wood/thermoplastic composites (WPCs) have been restricted in some fields of building construction and electrical equipment because of their inherent high flammability and lower toughness. In this work, a branched crosslinking network polyelectrolyte complex (PEC) has been designed by incorporation of polyethyleneimine (PEI), a [...] Read more.
Wood/thermoplastic composites (WPCs) have been restricted in some fields of building construction and electrical equipment because of their inherent high flammability and lower toughness. In this work, a branched crosslinking network polyelectrolyte complex (PEC) has been designed by incorporation of polyethyleneimine (PEI), a cation polyelectrolyte end capped amine groups, into cellulose nanocrystals (CNC), and ammonium polyphosphate (APP) via self-assembling. The hydrogen bonding interactions, penetration, and mechanical interlock provided by PEC effectively enhance the interfacial bonding within matrix, wood fibers, and flame retardant. Interestingly, it generates abundant micropores on the inner structure of WPC. The excellent interfacial bonding performance and easy-to-move molecular chain successfully transfer the stress and induce energy dissipation, simultaneously giving rise to higher strength and toughness for WPC. As well as the PEC endows WPC with a promotion in both smoke suppression and UL-94 V-0 rate. Additionally, the peak heat release rate and total smoke release for WPC obviously reduce by 36.9% and 50.0% respectively in presence of 25% PEC. A simple, eco-friendly, and concise strategy exhibits prospects for fiber-reinforced polymer composites with effective flame retardancy and mechanical robust properties. Full article
(This article belongs to the Collection Reinforced Polymer Composites)
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18 pages, 3272 KB  
Article
The Anomalous Influence of Polyelectrolyte Concentration on the Deposition and Nanostructure of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers
by Martin Müller
Molecules 2019, 24(11), 2141; https://doi.org/10.3390/molecules24112141 - 6 Jun 2019
Cited by 14 | Viewed by 4200
Abstract
The deposition and nanostructure of polyelectrolyte (PEL) multilayers (PEMs) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAA) onto silicon substrates was studied in terms of the dependence of pH and the PEL concentration (cPEL) in the individual adsorption steps z. Both a commercial automatic [...] Read more.
The deposition and nanostructure of polyelectrolyte (PEL) multilayers (PEMs) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAA) onto silicon substrates was studied in terms of the dependence of pH and the PEL concentration (cPEL) in the individual adsorption steps z. Both a commercial automatic dipping device and a homebuilt automatic stream coating device (flow cell) were used. Gravimetry, SFM, transmission (TRANS) and in situ attenuated total reflection (ATR) FTIR spectroscopy were used for the quantitative determination of the adsorbed amount, thickness, chemical composition and morphology of deposited PEMs, respectively. Firstly, the combination of pH = 10 for PEI and pH = 4 for PAA, where both PEL were predominantly in the neutral state, resulted in an extraordinarily high PEM deposition, while pH combinations, where one PEL component was charged, resulted in a significantly lower PEM deposition. This was attributed to both PEL conformation effects and acid/base interactions between basic PEI and acidic PAA. Secondly, for that pH combination an exponential relationship between PEM thickness and adsorption step z was found. Thirdly, based on the results of three independent methods, the course of the deposited amount of a PEM-10 (z = 10) versus cPEL in the range 0.001 to 0.015 M at pH = 10/4 was non-monotonous showing a pronounced maximum at cPEL = 0.005 M. Analogously, for cPEL = 0.005 M a maximum of roughness and structure size was found. Fourthly, related to that finding, in situ ATR-FTIR measurements gave evidence for the release of outermost located PEI upon PAA immersion (even step) and of outermost PAA upon PEI immersion (odd step) under formation of PEL complexes in solution. These studies help us to prepare PEL-based films with a defined thickness and morphology for interaction with biofluids in the biomedical and food fields. Full article
(This article belongs to the Special Issue The Progresses on Polyelectrolytes and Polyelectrolyte Complexes)
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