Properties Of Polyelectrolytes Research Articles

Does the Electrical Double Layer Contribute to the Mechanism of Action of Antimicrobial Peptides?

AbstractThis concept paper elucidates the possible influence of the electrical double layer (EDL) and the polyelectrolytic nature of bacterial cell walls on the behavior of antimicrobial peptides (AMPs) and lipopeptides. It proposes that the presence of EDL adjacent to lipid membranes may play a crucial role in inducing peptide aggregation and conformational changes, thus affecting their antimicrobial activity. Furthermore, it emphasizes that the negatively charged components in both Gram‐positive and Gram‐negative bacterial cell walls may act as polyelectrolytes, effectively reducing the critical micellization concentration (CMC) of positively charged peptides and lipopeptides. This reduction is expected to facilitate their aggregation, potentially enhancing their accumulation at the bacterial membrane and increasing their effectiveness in disrupting membrane integrity and exerting antimicrobial activity. Therefore, understanding the interplay between EDL effects, polyelectrolytic properties of bacterial cell walls, and the behavior of antimicrobial peptides is essential for elucidating their mechanisms of action and optimizing their therapeutic potential.

Engineering tribological rehydration of cartilage interfaces: Assessment of potential polyelectrolyte mechanisms

Articular cartilage, primarily composed of water and collagen, is vital for synovial joint function. Traditional hard biomaterials like ceramic or cobalt-chrome used in hemiarthroplasty often result in abnormal contact pressures and premature implant failure. This study investigates the tribological properties of polyelectrolyte functionalised PEEK (SPMK-g-PEEK) in contact with cartilage, proposing a solution to these issues by utilising tribological rehydration and effective aqueous lubrication.We demonstrate a new mode of polyelectrolyte enhanced tribological rehydration where SPMK-g-PEEK achieves low friction and promotes interstitial fluid recovery during sliding, independent of traditional hydrodynamic theories. This results in a rapid stabilisation of the coefficient of friction (CoF) to levels comparable to natural cartilage (CoF ∼ 0.01) and aids in approximately 8% cartilage strain recovery, indicating effective tribological rehydration even under cartilage degradation or altered osmotic conditions.Furthermore, we find that lubrication and rehydration against an SPMK-g-PEEK interface depend minimally on biphasic lubrication but significantly on the hydrophilic sulfonic acid groups of SPMK, which act as a fluid reservoir. Our findings suggest SPMK-g-PEEK as a promising biomaterial for cartilage interfacing implants that offer low friction and modulate cartilage interstitial fluid pressure. This study enhances our understanding of biotribological interactions and contributes to the development of joint replacement materials that support the natural function of cartilage.

Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect

Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect

Comb-like polyelectrolytes with pyridinium and trimethylammonium cations: Micellar catalytic and antibacterial properties

Here we report of two different but related properties of comb-like polyelectrolytes, namely, poly-11-acryloyloxyundecylpyridinium bromide and poly-11-acryloyloxyundecyltrimethylammonium bromide. The micellar catalytic activity of polyelectrolytes in alkali hydrolyses reactions of 4-nitrophenyl ethers and their antibacterial activity against Escherichia coli and Staphylococcus aureus were the focus of this work. A comparative analysis on the declared properties of a comb-like polyelectrolyte vs monomer and a non-polymerizable surfactant were carried out. The influence of the ionic strength on the solubilization and the catalytic activity of comb-like polyelectrolytes were studied. The catalytic activity of comb-like polyelectrolytes is several times higher than that for low-molecular analogs. The largest differences are observed at low catalyst concentrations. Antibacterial activity of monomers and polymers against staphylococci and escherichia using drip method was revealed. Investigated polyelectrolytes have generally order of magnitude lower inhibitory concentrations in E. coli compared to their monomers. Only one of the polymers synthesized by us turned out to be active against staphylococci.

Exclusion liquid chromatography of carboxymethylchitin and carboxymethylchitosan from crustacean <i>Artemia Parthenogenetica</i> of the Aral Sea

The article deals with the synthesis of water-soluble derivatives of chitin and chitosan from cysts of crustaceans of the genus Artemia Parthenogenetica of the Aral Sea by carboxymethylation of OH and NH2 groups of their chains. The elution, viscosity and polyelectrolyte properties in size exclusion liquid chromatography of carboxymethylchitin and carboxymethylchitosan were studied. The suppression of electrostatic effects and the implementation of the exclusion mechanism for the separation of these polysaccharides were achieved by using an aqueous solution of sodium nitrate with a concentration of 0.1 mol/l as an eluent, which was recommended for determining molecular weight characteristics.

Polyhydroxyurethane and Poly(ethylene oxide) Multiblock Copolymer Networks: Crosslinking with Polysilsesquioxane, Reprocessing and Solid Polyelectrolyte Properties.

This contribution reports the synthesis of polyhydroxyurethane (PHU)-poly(ethylene oxide) (PEO) multiblock copolymer networks crosslinked with polysilsesquioxane (PSSQ). First, the linear PHU-PEO multiblock copolymers were synthesized via the step-growth polymerization of bis(6-membered cyclic carbonate) (B6CC) with α,ω-diamino-terminated PEOs with variable molecular weights. Thereafter, the PHU-PEO copolymers were allowed to react with 3-isocyanatopropyltriethoxysilane (IPTS) to afford the derivatives bearing triethoxysilane moieties, the hydrolysis and condensation of which afforded the PHU-PEO networks crosslinked with PSSQ. It was found that the PHU-PEO networks displayed excellent reprocessing properties in the presence of trifluoromethanesulfonate [Zn(OTf)2]. Compared to the PHU networks crosslinked via the reaction of difunctional cyclic carbonate with multifunctional amines, the organic-inorganic PHU networks displayed the decreased reprocessing temperature. The metathesis of silyl ether bonds is responsible for the improved reprocessing behavior. By adding lithium trifluoromethanesulfonate (LiOTf), the PHU-PEO networks were further transformed into the solid polymer electrolytes. It was found that the crystallization of PEO chains in the crosslinked networks was significantly suppressed. The solid polymer electrolytes had the ionic conductivity as high as 7.64 × 10-5 S × cm-1 at 300 K. More importantly, the solid polymer electrolytes were recyclable; the reprocessing did not affect the ionic conductivity.

Preparation of Gelatin-Quaternary Ammonium Salt Coating on Titanium Surface for Antibacterial/Osteogenic Properties.

Titanium (Ti) and its alloys are widely used in medical treatment, engineering, and other fields because of their excellent properties including biological activity, an elastic modulus similar to that of human bones, and corrosion resistance. However, there are still many defects in the surface properties of Ti in practical applications. For example, the biocompatibility of Ti with bone tissue can be greatly reduced in implants due to a lack of osseointegration as well as antibacterial properties, which may lead to osseointegration failure. To address these problems and to take advantage of the amphoteric polyelectrolyte properties of gelatin, a thin layer of gelatin was prepared by electrostatic self-assembly technology. Diepoxide quaternary ammonium salt (DEQAS) and maleopimaric acid quaternary ammonium salt (MPA-N+) were then synthesized and grafted onto the thin layer. The cell adhesion and migration experiments demonstrated that the coating has excellent biocompatibility, and those grafted with MPA-N+ promoted cell migration. The bacteriostatic experiment showed that the mixed grafting with two ammonium salts had excellent bacteriostatic performance against Escherichia coli and Staphylococcus aureus, with bacteriostasis rates of 98.1 ± 1.0% and 99.2 ± 0.5%, respectively.

An amphiphilic flocculant with a lignin core for efficient separation of suspended solids

The synthesis and application of conventional polymeric flocculants suffer from low flocculation efficiency and toxic residues; therefore, there is an urgent need to develop green and efficient flocculants and corresponding technologies. An amphiphilic copolymer (NPL) was synthesized by a “grafting to” strategy, using acrylamide, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and kraft lignin. NPL consists of a lignin core that is attached to a polyacrylamide branched chain and a cationic group, and has the properties of an amphoteric polyelectrolyte. This structure demonstrates superior flocculation performance on suspended solids. Two typical clay suspensions, kaolin and bentonite, were selected to evaluate the flocculation performance of NPL. The results showed that the turbidity of kaolin and bentonite could be reduced to 2.08 NTU and 0.31 NTU, respectively, by using NPL in combination with polymeric aluminum chloride. The synergistic effect of charge neutralization and bridging was confirmed as the main mechanism of flocculation on the two clay suspensions by a series of characterization techniques, such as zeta potential determination, particle size analysis, and focused beam reflectance measurement. The treatment of high-turbidity wastewater/feedwater with NPL was investigated, and was found to significantly improve the effluent quality. The use of NPL is efficient, environmentally friendly, and technically feasible, and shows excellent potential for the treatment of wastewater.

Research Progress of the Ion Activity Coefficient of Polyelectrolytes: A Review.

Polyelectrolyte has wide applications in biomedicine, agriculture and soft robotics. However, it is among one of the least understood physical systems because of the complex interplay of electrostatics and polymer nature. In this review, a comprehensive description is presented on experimental and theoretical studies of the activity coefficient, one of the most important thermodynamic properties of polyelectrolyte. Experimental methods to measure the activity coefficient were introduced, including direct potentiometric measurement and indirect methods such as isopiestic measurement and solubility measurement. Next, progress on the various theoretical approaches was presented, ranging from analytical, empirical and simulation methods. Finally, challenges for future development are proposed on this field.

Synthesis of polycationic nanoparticles for microbial inhibition and killing.

Antimicrobial polymers (AMP) appear to be a promising candidate to deal with the current scenario of bacterial resistance against conventional drugs and antibiotics as they mainly depend on disrupting the bacterial membrane. This work investigates the effect of polycations bearing aromatic and aliphatic pendant cationic groups on the antimicrobial performance of AMP. A radical polymerization strategy was adopted to synthesize two different copolymers and convert them into polycations upon post-modification. Polyelectrolytes were converted into nanoparticles by nanoprecipitation and named PE1 and PE2. Polymers were analyzed by NMR, FT-IR, and gel permeation chromatography (GPC). PE1 and PE2 nanoparticles were uniform, spherical particles from FESEM, size, and zeta potential measurements. The antimicrobial properties of polyelectrolytes were determined against pathogenic Escherichia coli (E. coli), Bacillus Subtilis (B. Subtilis), Bacillus Amyloliquefaciens (B. Amyloliquefaciens) and Citrobecter Freundii (C. Freundii) bacterias. The biocidal activity determination studies showed that polyelectrolyte PE2 with aromatic pendant units outperformed PE1 with the aliphatic pendant group. This work highlights the remarkable effect of aromatic segmentation, which provides microbial inhibition, and killing is demonstrated as an antibacterial surface coating.

One‐step synthesis of silver nanoparticles exposed on the chitosan‐covered polyamide 6 electrospinning nanofibers

AbstractA one‐step method was developed for synthesizing Ag nanoparticles exposed on the chitosan‐covered polyamide 6 (CS‐Ag@PA6) nanofibers by the in‐situ reduction of silver nitrate during the electrospinning process. The bioderived CS was employed as a stabilizer and chelating carrier of Ag0/Ag+ through its functional groups. CS was also used as a tractive agent to promote the surface migration of Ag atoms owing to its polyelectrolytic properties and immiscibility with PA6. Formic acid was used as the co‐solvent for PA6 and CS and the reducing agent for Ag+. It was verified that the Ag nanoparticles (AgNPs) with 31.7% Ag0 were embedded inside the pure PA6 nanofibers. However, the incorporation of CS achieved the AgNPs with an improved reduction efficiency (i.e., 67.5% of Ag0). In particular, the CS nanolayers were covered on the PA6 nanofiber skeleton, where the AgNPs migrated on the surface of the CS nanolayers. This surface migration of CS and AgNPS endowed a significantly enhanced catalytic activity to the reduction of 4‐nitrophenol, where the reduction rate constant (k) and turnover frequency (TOF) were an order of magnitude higher than that of the CS‐free nanofibers.

Amylose content and pre-freezing regulate the structure and oil absorption of polyelectrolytes-based starch cryogel

Starch cryogel is a potential material for oil absorption. This study provided a facile and convenient polyelectrolyte-based preparation strategy of starch cryogel, in which the structural properties of the cryogel were regulated by amylose content and pre-freezing without long-time retrogradation. Sodium laurate was used as a guest model to form starch-fatty acid salt complex (polyelectrolyte). The amount of amylose content and sodium laurate added led more polyelectrolytes, significantly increased V-type crystallinity from 3.72 % to 22.40 % and complexing index from 4.32 % to 28.48 %. As the uniform pore structure improved the oil absorption ability of starch cryogel, the starch cryogel prepared by waxy maize starch followed by quick pre-freezing showed the highest specific surface area (9.87 m2/g) and oil absorption capacity (32.94 g/g). Our findings suggest that polyelectrolyte properties have great potential in the preparation of starch-based cryogels, which could be applied in the design of novel starch-based porous materials.

Effect of Cationic Modified Microcrystalline Cellulose on the Emulsifying Properties and Water/Oil Interface Behavior of Soybean Protein Isolate.

Stabilizing emulsion using complex biopolymers is a common strategy. It would be very interesting to characterize the impact of charge density on the emulsifying properties of complex polyelectrolytes carrying opposite charges. In this study, cationic modified microcrystalline celluloses (CMCC) of different charge densities were prepared and mixed with soy protein isolate (SPI) for emulsion applications. CMCC-1 to 3 with various cationic charge values were successfully prepared as characterized by zeta-potential and FTIR. The positive charge density’s effects on solubility, thermogravimetric properties, and rheological properties were studied. Complexes of SPI-CMCC with various zeta-potential values were then obtained and used to stabilize soybean oil emulsions. The results show that emulsions stabilized by complexes of SPI and CMCC-3 at a ratio of 1:3 had the best emulsification ability and stability. However, the interfacial tension-reducing ability of complexes decreased continuously with increasing cationic charge value, while the rheological results show that complexes of SPI-CMCC-3 at a ratio of 1:3 formed a stronger viscoelastic network than other complexes. Our results indicate that this SPI-CMCC complex formula showed excellent emulsification performance, which could be adjusted and promoted by changing the charge density. This complex formula is promising for fabrication of emulsion-based food and cosmetic products.

Design of co-continuous structure of cellulose/PAA-based alkaline solid polyelectrolyte for flexible zinc-air battery

In order to prepare high ionic conductivity and robust mechanical properties of alkaline solid polyelectrolyte (ASPE) for applications in flexible wearable devices, a co-continuous structure membrane was designed using in-situ polymerization to introduce cross-linked polyacrylic acid (N-PAA) into the cellulose network constructed by regenerated degreasing cotton (RDC). The resultant ASPE membrane showed high ionic conductivity (430 mS·cm−1 at 25 °C), strong mechanical properties, and excellent alkaline stabilities, proving the viability of cellulose for use in energy storage systems. Surprisingly, the sandwich-shaped zinc-air battery assembled using RDC/N-PAA/KOH membranes as electrolytes exhibits superior values of cycling stability, discharge time, specific capacity (731.5 mAh·g−1), peak power density (40.25 mW·cm−2), and mechanical flexibility. Even under bending conditions, the zinc-air batteries still possess stable energy supply performance, suggesting this novel solid polyelectrolyte has promising application for wearable technology.

Membrane stiffening in Chitosan mediated multilamellar vesicles of alkyl ether carboxylates

HypothesisMembrane undulations are known to strongly affect the stability of uni- and multilamellar vesicles formed by surfactants or phospholipids. Herein, based on the same arguments, we hypothesise that the properties of polyelectrolyte mediated surfactant multilamellar vesicles, in particular the multiplicity – i.e. the number of layers forming the vesicle – depend on the dynamics of the membrane. ExperimentsSmall-angle neutron scattering (SANS) and neutron spin-echo (NSE) were used to probe the structure and the dynamics of the multilayered vesicles formed in mixtures of the biopolymer chitosan and oppositely charged alkyl ether carboxylates. The neutron scattering data are complemented by static and dynamic light scattering experiments. Experiments were performed in polyelectrolyte excess conditions, and at a pH close to the pKa of the surfactant. FindingsThe structural investigation shows very clearly that multilayered surfactant/polyelectrolyte vesicles are formed in the investigated mixtures. Only 3 to 5 layers form, on average, one vesicle, as similarly found in mixtures of chitosan and phospholipid vesicles. NSE shows that the surfactant membrane becomes stiffer upon complexation with chitosan, and that the fluctuation of the layers is strongly coupled in time and space. Such strong coupling and the increase in overall stiffness is associated with a high entropic cost. Accordingly, the combined SANS and NSE study points out that the low multiplicity found in multilayered vesicles involving the rigid polysaccharide chitosan arises from the strongly coupled dynamics of the membrane layers.

Hydrodynamic and Polyelectrolyte Properties of Actin Filaments: Theory and Experiments.

Actin filament’s polyelectrolyte and hydrodynamic properties, their interactions with the biological environment, and external force fields play an essential role in their biological activities in eukaryotic cellular processes. In this article, we introduce a unique approach that combines dynamics and electrophoresis light-scattering experiments, an extended semiflexible worm-like chain model, and an asymmetric polymer length distribution theory to characterize the polyelectrolyte and hydrodynamic properties of actin filaments in aqueous electrolyte solutions. A fitting approach was used to optimize the theories and filament models for hydrodynamic conditions. We used the same sample and experimental conditions and considered several g-actin and polymerization buffers to elucidate the impact of their chemical composition, reducing agents, pH values, and ionic strengths on the filament translational diffusion coefficient, electrophoretic mobility, structure factor, asymmetric length distribution, effective filament diameter, electric charge, zeta potential, and semiflexibility. Compared to those values obtained from molecular structure models, our results revealed a lower value of the effective G-actin charge and a more significant value of the effective filament diameter due to the formation of the double layer of the electrolyte surrounding the filaments. Contrary to the data usually reported from electron micrographs, the lower values of our results for the persistence length and average contour filament length agree with the significant difference in the association rates at the filament ends that shift to sub-micro lengths, which is the maximum of the length distribution.

Interactions on Proteins Arising from the Self-Assembly of a Polyelectrolyte Brush.

Surfaces grafted with polyelectrolyte chains for excellent performance in protein antifouling are highly desired in many applications, such as biomedical implants and devices. In general, the adsorbing/resisting behaviors of proteins can be mainly attributed to the electrostatic interactions that are associated with the charge properties of proteins and polyelectrolytes. By coarse-grained molecular dynamics simulations, we examined the self-assembled structures of polyanion and polyzwitterion brushes as well as the interactions on negatively and positively charged proteins. We found that in addition to charges, the structural polarization induced by self-assembly with a certain charge distribution shows significant influences on protein behavior. The large-scale dipole-dipole interactions between brushes and proteins can dominate the behavior of proteins on the brushes under certain circumstances. To ensure simulation accuracy, we compared two models and found a polar Martini model that explicitly treats electrostatic interactions as long-ranged ones, giving a more reasonable structural description compared with the normal Martini model that truncates electrostatic interactions.

Cationic Polyelectrolytes Containing Perfluorinated Groups: Synthesis and Self-Assembly Properties in Aqueous Solutions

In this work, the synthesis and solution self-assembly of partially fluorinated cationic polyelectrolytes based on post-polymerization-modified poly(2-(dimethylamino) ethyl methacrylate), incorporating hydrophobic fluorinated groups along the polymer chain, is reported. The post-polymerization modification aims to establish amphiphilic characteristics and strong polyelectrolyte properties to the polymer. Therefore, the self-organization characteristics in aqueous media are expected to be affected. The poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) homopolymer precursor is synthesized using RAFT polymerization. A quaternization reaction on the amine side groups using heptadecafluoro-10-iododecane results in the poly((2-dimethylamino) ethyl methacrylate-co-quaternized heptadecafluoro-10-iododecane (2-dimethylamino) ethyl methacrylate) (PQFD) amphiphilic statistical copolymers. We intentionally study statistical copolymers in our research of DMAEMA-based polyelectrolytes as there are not many studies about such materials. We have also chosen the incorporation of highly hydrophobic perfluorinated groups to study the changes in the solution properties of the initial hydrophilic homopolymer. The successful synthesis is supported by size-exclusion chromatography (SEC), 1H-NMR, and FTIR experiments. The self-assembly of the copolymers in aqueous solutions along with the dependence of the properties of the resulting aggregates on the pH, temperature, and ionic strength of the solution are studied using light scattering methods (DLS, ELS) and fluorescence spectroscopy (FS). The structural characteristics of the aggregates depend on composition, solution preparation protocol and solution pH, and temperature.

Theory of Weakly Polydisperse Cytoskeleton Filaments.

Cytoskeleton filaments have the extraordinary ability to change conformations dynamically in response to alterations of the number density of actins/tubulin, the number density and type of binding agents, and the electrolyte concentration. This property is crucial for eukaryotic cells to achieve specific biological functions in different cellular compartments. Conventional approaches to biopolymers’ solution break down for cytoskeleton filaments because they entail several approximations to treat their polyelectrolyte and mechanical properties. In this article, we introduce a novel density functional theory for polydisperse, semiflexible cytoskeleton filaments. The approach accounts for the equilibrium polymerization kinetics, length and orientation filament distributions, as well as the electrostatic interaction between filaments and the electrolyte. This is essential for cytoskeleton polymerization in different cell compartments generating filaments of different lengths, sometimes long enough to become semiflexible. We characterized the thermodynamics properties of actin filaments in electrolyte aqueous solutions. We calculated the free energy, pressure, chemical potential, and second virial coefficient for each filament conformation. We also calculated the phase diagram of actin filaments’ solution and compared with the corresponding results in in vitro experiments.

Counterion distribution around a polyelectrolyte confined in a metal–organic framework

ABSTRACT Recently, polyelectrolytes confined in metal–organic frameworks (MOFs) are reported to demonstrate superior ion exchange with high selectivity. To reveal the counterion distribution around spatially confined polyelectrolytes without direct experimental measurements, we perform molecular dynamics simulations of ionic solution in equilibrium with a polyelectrolyte–MOF composite in explicit water. In contrast to the reported qualitative work on linear polymer conformation in vacuum, polyelectrolytes behave as stiff-like polymers after threading into the one-dimensional channels of MIL-53(Al). Consequently, the counterions tend to be uniformly distributed and locally condensed around the linearised polyelectrolyte chain. In addition to the high ion exchange performance properties of polyelectrolyte–MOF composites, the unique distribution of counterions and the structural dynamics of the confined polyelectrolyte would lead to other potential applications in membranes and interfacial technologies.