Formation Of Interpolyelectrolyte Complexes Research Articles

Hybrid nanoreactors formed by interpolyelectrolyte complex formation: a colloidal platform for light-driven catalysis

Micellar interpolyelectrolyte complexes are introduced as versatile soft matter matrices for light-driven hydrogen evolution catalysis.

СУДА ЕРИТІН ПОЛИМЕРЛЕР МЕН ОЛАРДЫҢ ПОЛИКОМПЛЕКСТЕРІНІҢ СУЛЫ ЕРІТІНДІДЕГІ ҚАСИЕТТЕРІ

Abstract. The interaction of oppositely charged polyelectrolytes (sodium salt of carboxymethylcellulose (NaCMC), methylcellulose (MC), polyethylenimine (PEI) and polydimethyldiallylammonium chloride (PDMDAAС), and unifloc (UF)) in an aqueous environment was studied using the methods of viscometry, spectrophotometry and macroelectrophoresis. It has been established that the interaction of these polyelectrolytes is accompanied by a significant decrease in reduced viscosity (up to 0.1-0.15 dl/g, which is typical for compacted macromolecules of globular proteins), an increase in optical density and an inversion of the sign of the electrokinetic potential. All this indicates the formation of interpolymer complexes from interacting cationic and anionic polyelectrolytes. Experimental results of studying the properties of water soluble polymers and their polyelectrolyte complexes in aqueous solutions at the water/air interface are described and discussed. It has been shown that complex formation in relatively simple systems is accompanied by changes in the pH of the medium, optical, hydrodynamic, electrochemical and other properties of macromolecules. In the systems we studied, the interaction of the system components is not accompanied by variations in the pH of the medium, therefore, information about the interaction of water-soluble polyelectrolytes in the systems we studied was obtained based on viscometric and spectrophotometric titration data, as well as from changes in the electrokinetic potential of macromolecules. The study of the electrokinetic potential showed that the formation of interpolymer complexes in the systems under consideration is accompanied by significant changes in the electrokinetic potential of macromolecules. A study of the properties of mixtures of aqueous solutions of Na-CMC, MC, UF with polydimethyldiallylammonium chloride and polyethylenimine indicates the formation of interpolyelectrolyte complexes that have a more compact structure than the original macromolecules. Key words: polyelectrolytes; flocculation; cross-linking; stability; interpolymer complexes; optical density; polymer.

Ag2O-Containing Biocidal Interpolyelectrolyte Complexes on Glass Surfaces-Adhesive Properties of the Coatings.

Biocidal coatings are of great interest to the healthcare system. In this work, the biocidal activity of coatings based on a complex biocide containing polymer and inorganic active antibacterial components was studied. Silver oxide was distributed in a matrix of a positively charged interpolyelectrolyte complex (IPEC) of polydiallyldimethylammonium chloride (PDADMAC) and sodium polystyrene sulfonate (PSS) using ultrasonic dispersion, forming nanoparticles with an average size of 5-6 nm. The formed nanoparticles in the matrix are not subject to agglomeration and changes in morphology during storage. It was found that the inclusion of silver oxide in a positively charged IPEC allows a more than 4-fold increase in the effectiveness of the complex biocide against E. coli K12 in comparison with the biocidal effect of PDADMAC and IPEC. Polycation, IPEC, and the IPEC/Ag2O ternary complex form coatings on the glass surface due to electrostatic adsorption. Adhesive and cohesive forces in the resulting coatings were studied with micron-scale coatings using dynamometry. It was found that the stability of the coating is determined primarily by adhesive interactions. At the macro level, it is not possible to reliably identify the role of IPEC formation in adhesion. On the other hand, use of the optical tweezers method makes it possible to analyze macromolecules at the submicron scale and to evaluate the multiple increase in adhesive forces when forming a coating from IPEC compared to coatings from PDADMAC. Thus, the application of ternary IPEC/Ag2O complexes makes it possible to obtain coatings with increased antibacterial action and improved adhesive characteristics.

Electrochemical detection of lead and cadmium ions in water by sensors based on modified track-etched membranes

Electrochemical sensors based on PET track-etched membranes (TeMs) were prepared by photograft polymerization of 2-hydroxyethylmethacrylate (HEMA) and subsequent formation of interpolyelectrolyte complexes with poly(allylamine) (PAlAm). The functionalized TeMs were characterized by scanning electron microscopy (SEM), FTIR spectroscopy, gas permeability and colorimetric assay. Parameters of graft polymerization such as monomer concentration, time of irradiation, solvent and others were estimated and optimized. Cd(II) and Pb(II) ions were detected by using square wave anodic stripping voltammetry (SW-ASV). Additional modification of the modified membranes with 4-mercaptophenylboronic acid (MPBA) led to increasing of stability of the sensors. The linear range for the detection of Cd(II) and Pb(II) ions using the modified electrode was 50 µg - 4.25 mg/L and 10 µg – 4.25 mg/L. Moreover, the obtained results of SW-ASV demonstrated that the enhancement in the electrochemical signals was achieved with PET TeMs-g-PHEMA-PAlAm\MPBA compared to that of a bare PET TeMs-g-PHEMA. Selectivity test showed that alkali and alkaline earth metal ions, except for magnesium (up to 1 mg/l), do not particularly interfere with the determination of lead and cadmium in the analyte. Sensing of Pb and Cd ions in river water demonstrate us that prepared sensors can be used in real conditions with sufficient accuracy and reproducibility of the results.

WATER-SOLUBLE INTERPOLYELECTROLYTE COMPLEX BASED ON POLY(DIALLYLDIMETHYLAMMONIUM CHLORIDE) AND SODIUM POLYACRYLATE AS A COMPONENT FOR CREATING STABLE BIOCIDAL COATINGS

Polycation-based coatings represent a promising class of protective antimicrobial coatings. Water-soluble complexes of poly(diallyldimethylammonium chloride) (PDADMAC) with sodium polyacrylate (PANa) have been studied by turbidimetry. It has been shown that the addition of the polyanion (12 mol %) to the polycation leads to the formation of an interpolyelectrolyte complex (IPEC) stable with respect to phase separation in water-salt media with salt concentrations as high as 0.1–0.2 M. In contrast to the traditional method of obtaining coatings from IPEC by layer-by-layer deposition, we have studied the preparation of the coatings directly from a solution of water-soluble IPEC on a hydrophilic glass surface and a surface of more hydrophobic polycarbonate. It has been found that the formation of IPEC makes it possible to increase the resistance of the coating to wash-off with water compared to the individual PDADMAC coating on both types of substrates.

Nano-Sized Fucoidan Interpolyelectrolyte Complexes: Recent Advances in Design and Prospects for Biomedical Applications.

The marine polysaccharide fucoidan (FUC) is a promising polymer for pharmaceutical research and development of novel drug delivery systems with modified release and targeted delivery. The presence of a sulfate group in the polysaccharide makes FUC an excellent candidate for the formation of interpolyelectrolyte complexes (PECs) with various polycations. However, due to the structural diversity of FUC, the design of FUC-based nanoformulations is challenging. This review describes the main strategies for the use of FUC-based PECs to develop drug delivery systems with improved biopharmaceutical properties, including nanocarriers in the form of FUC-chitosan PECs for pH-sensitive oral delivery, targeted delivery systems, and polymeric nanoparticles for improved hydrophobic drug delivery (e.g., FUC-zein PECs, core-shell structures obtained by the layer-by-layer self-assembly method, and self-assembled hydrophobically modified FUC particles). The importance of a complex study of the FUC structure, and the formation process of PECs based on it for obtaining reproducible polymeric nanoformulations with the desired properties, is also discussed.

The study of interactions between textile auxiliary polyelectrolytes by isothermal titration calorimetry

• Interactions between cationic and anionic polyelectrolytes. • Thermodynamic characteristics of micellization. • Isothermal titration calorimetry study. The interactions between the cationic polyelectrolyte poly(dimethyldiallyl ammonium chloride) (VPK-402, PDADMAC) and the anionic polyelectrolyte Acremon B-1 (Ac), widely used as auxiliary materials in the textile industry, as well as Ac aggregation have been studied by isothermal titration calorimetry. The thermodynamic characteristics of Ac micelle formation and of interpolyelectrolyte complex formation between Ac and VPK-402 have been obtained in an aqueous solution at 298.15 K. It has been revealed that the entropy factor was favorable to the Ac micellization process. It has been found that at a low concentration of Ac in a solution, the interaction between Ac and VPK-402 was also controlled by the entropy contribution. On the contrary, the formation of Ac – VPK-402 interpolyelectrolyte complexes at high Ac concentrations was enthalpycally favorable.

Modification of Polydiallyldimethylammonium Chloride with Sodium Polystyrenesulfonate Dramatically Changes the Resistance of Polymer-Based Coatings towards Wash-Off from Both Hydrophilic and Hydrophobic Surfaces.

Polymer coatings based on polycations represent a perspective class of protective antimicrobial coatings. Polydiallyldimethylammonium chloride (PDADMAC) and its water-soluble complexes with sodium polystyrenesulfonate (PSS) were studied by means of dynamic light-scattering, laser microelectrophoresis and turbidimetry. It was shown that addition of six mol.% of polyanion to polycation results in formation of interpolyelectrolyte complex (IPEC) that was stable towards phase separation in water-salt media with a concentration of salts (NaCl, CaCl2, Na2SO4, MgSO4) up to 0.5 M. Most of the polyelectrolyte coatings are made by layer-by-layer deposition. The utilization of water-soluble IPEC for the direct deposition on the surface was studied. The coatings from the PDADMAC and the PSS/PDADMAC complex were formed on the surfaces of hydrophilic glass and hydrophobic polyvinylchloride. It was found that formation IPEC allows one to increase the stability of the coating towards wash-off with water in comparison to individual PDADMAC coating on both types of substrates. The visualization of the coatings was performed by atomic force microscopy and scanning electron microscopy.

Interpolymer Complex of Chitosan and Eudragit L-100: Preparation, Characterization and Drug Release Behavior

Aims: The aim of the present investigation was to prepare interpolymer complex between Chitosan and Eudragit L100, and to evaluate its performance as a matrix for controlled release of drugs, using Diclofenac sodium as a model.
 Methodology: Interpolymer complex were prepared by combining different % chitosan solutions with different % Eudragit L100 solutions in different ratios. The formation of interpolyelectrolyte complexes (IPEC) between carbopol and Chitosan was investigated, using turbidimetry and viscosity measurement. The structure of the prepared IPEC was investigated using FTIR spectroscopy and DSC. A Rotary compression press was used to formulate matrix tablets of diclofenac sodium using polymers in physical mixture and IPECs.The amount of Diclofenac Sodium released in the dissolution medium was determined spectrophotometrically at 276 nm.
 Results: The results of the present investigation confirmed the formation of an interpolyelectrolyte complex between Chitosan and Eudragit L 100. The release of the model drug Diclofenac sodium was significantly controlled from tablets made up of the IPEC as compared with polymers alone and in combination. Release profiles were represented by a mathematical model, which indicates that the prepared system releases drug in a zero-order manner by changing the ratio of the IPEC in the tablets.
 Conclusion: Controlled release drug delivery systems designed to manipulate the drug release to achieve specific clinical objectives that are unattainable with conventional dosage forms.

Enhancement of electrochemical detection of Pb2+ by sensor based on track-etched membranes modified with interpolyelectrolyte complexes

This article concerns studies of flexible track-etched membrane modification by photograft polymerization of methacrylic acid and subsequent formation of interpolyelectrolyte complexes with poly(allylamine) for enhancement of properties of electrochemical sensor. Optimal conditions leading to functionalization of the surface and maintenance of the pore structure were found. Membranes were characterized by SEM, FTIR, XPS, gas permeability and colorimetric assay. Square wave anodic stripping voltammetry (SW-ASV) was used for detection of Pb2+. Limits of detection (LOD) for sensors based on non-modified PET TeMs, membranes modified by graft polymerization of methacrylic acid (PET TeMs-g-PMAA) and membranes modified with interpolyelectrolyte complexes with poly(allylamine) (PET TeMs-g-PMAA-PAlAm) are 3.03, 2.78 and 1.25 µg/L, respectively. Thus, it was shown that the formation of interpolyelectrolyte complexes on the membranes leads to a more accurate detection of lead ions.

Soil structuring using interpolyelectrolyte complexes of water‐soluble polysaccharides

Soil degradation is an important problem on a global scale. Suitable materials for its solution are interpolyelectrolyte complexes (IPEC) of biodegradable polymers. IPEC based on the oppositely charged pairs of biodegradable polymers—chitosan and sodium alginate (Ch‐SA), chitosan and sodium carboxymethylcellulose (Ch‐SC), and chitosan‐gellan gum (Ch‐GG) were prepared and studied using different physicochemical techniques (FTIR‐spectroscopy, dynamic light scattering, conductometric and turbidimetric titration, and rheoviscometric measurements). Thin films of IPECs were prepared by pouring polymer solutions on a flat surface and subsequent evaporation of water. These films were tested using mechanical analysis. Young modulus of IPEC films increases in the following order: Ch‐SC < Ch‐GG < Ch‐SA. Urban soil samples were sequentially treated with Ch solution and negatively charged polymer solution (SC, SA, GG). This technique of soil treatment leads to formation of IPEC within the soil surface layer. The soil structures and also soil treated with pure water and individual polymer solutions were also tested using mechanical analysis. It was found that the most durable structures are formed by IPEC based on Ch and SC. All the applied systems can be arranged in the following sequence in ascending order of the Young's modulus: GG < Ch < SA < Water < SC < Ch‐GG < Ch‐SA < Сh‐SC. The IPEC based on biodegradable and biocompatible polymers of polysaccharide nature can be successfully used for soil structuring. These polymers significantly increase the mechanical strength of the soil without harmful effects to the environment. Among the studied systems, the Ch‐SC system has the greatest structuring ability. These soil structuring agents can be applied for improving of the quality of urban and agricultural soils.

Synthesis and Properties of Chitosan- and Pectin-Based Hydrogels

Hydrogels have been prepared by mixing chitosan and pectin solutions, as well as solutions of their modified derivatives, in aqueous media at room temperature. The gels are obtained within a time period from several seconds to half an hour or more, depending on the process conditions. The hydrogels are formed due to both the covalent bonding between functional groups and the formation of interpolyelectrolyte complexes via the interaction between ammonium groups of chitosan and carboxylate groups of pectin. Conditions have been determined for the hydrogel formation throughout the solution volume without liquid phase separation. The swelling of lyophilized hydrogels has been studied as depending on the ionic strength and pH of aqueous media. The feasibility of prolonged drug release from the developed polymer matrix has been shown by the example of cytostatics, namely, mitomycin C and cisplatin.

Preliminary investigation on a new natural based poly(gamma-glutamic acid)/Chitosan bioink.

The study aims to investigate a novel bioink made from Chitosan (Cs)/ poly(gamma-glutamic acid) (Gamma-PGA) hydrogel that takes advantage of the two biodegradable and biocompatible polymers meeting most of the requirements for biomedical applications. The bioink could be an alternative to other materials commonly used in 3D-bioprinting such as gelatin or alginate. Cs/ Gamma-PGA hydrogel was prepared by double extrusion of Gamma-PGA and Cs solutions, where 2 × 105 human adult fibroblasts per ml Cs solution had been loaded, through Cellink 3D-Bioprinter at 37°C. A computer aided design model was used to get 3D-bioprinting of a four layers grid hydrogel construct with 70% infill. Hydrogel characterization involved rheology, FTIR analysis, stability study (mass loss [ML], fluid uptake [FU]), and cell retaining ability into hydrogel. 3D-bioprinted hydrogel gelation time resulted to be <60 s, hydrogel structure was maintained up to 36.79 Pa shear stress, FTIR analysis demonstrated Gamma-PGA/Cs interpolyelectrolyte complex formation. The 3D-bioprinted hydrogel was stable for 35 days (35% ML) in cell culture medium, with increasing FU. Cell loaded 3D-bioprinted Cs 6% hydrogel was able to retain 70% of cells which survived to printing process and cell viability was maintained during 14 days incubation.

Formation of the structure of interpolyelectrolyte complex in solid state: Role of comb-like amphiphilic polyelectrolyte

Interpolyelectrolyte complexes (IPECs) were obtained from linear polyanion poly (2-acrylamido-2-methylpropanesulfonic acid) (pAMPS) and comb-like polycation poly(11-acryloyloxyundecyltrimethylammonium) bromide (pAUTA-Br) using different strategies comprising of mixing polyelectrolyte solutions in homogeneous and heterogeneous conditions and the polymerization of ionic monomer in the presence of opposite-charged polyelectrolyte. The supramolecular structure of IPEC in a solid state was studied by SAXD. The hexagonal or cubic order was revealed by IPEC obtained in different conditions. The lattice unit cell size appeared to be dependent on the solvent thermodynamic quality of the used polymers. These structures are pre-formed in solutions of comb-like self-organized components and fixed in a solid state in the course of kinetically driven IPEC formation.

Features of the Formation of Interpolyelectrolyte Complexes Based on Chitosan and Pectin

Conditions for the preparation of stable to sedimentation aqueous dispersions of interpolyelectrolyte complexes based on chitosan (Chit) and pectin (Pect) with particle diameter 0.5-0.9 μm for Pect/Chit and 1.0-2.0 μm for Chit/Pect have been determined. The absolute value of the zeta potential of these complexes is >10 mV for Pect/Chit and Chit/Pect when the molar ratio of the ionogenic groups of the polymers $$ {n}_{\mathrm{COOH}}/{n}_{{\mathrm{NH}}_2} $$ is 0.4-4.6 for Pect/Chit and 0.02-0.63 for Chit/Pect. Optical spectroscopy and electrophoretic light scattering have been used to determine the effect of molecular mass and the content of the free ionogenic groups in the polysaccharide macromolecules as well as the order of mixing the solution on the formation and properties of these interpolyelectrolyte complexes.

Fluorine-containing block/branched polyamphiphiles forming bioinspired complexes with biopolymers.

Colloidal-chemical characteristics of block/branched cationic and non-ionic polyamphiphiles containing poly(fluorine-alkyl methacrylate) (poly(FMA)) block and their intermolecular complexes with biopolymers were studied. The dependences of their surface activity and micelle size on the length of hydrophobic and hydrophilic blocks, as well as the length of side fluorine-alkyl branches were established. Poly(FMA)-block-poly(DMAEMA) was used for formation of interpolyelectrolyte complexes with plasmid DNA (pDNA) via their electrostatic interaction. Novel non-viral polyplexes were tested as gene delivery systems for mammalian cells. The results of DLS, TEM and MALDI-ToF studies demonstrated disaggregation of lysozyme (LYZ) aggregates in the presence of poly(FMA)-block-poly(NVP) and formation of the polyamphiphile…LYS complex possessing antibacterial action.

Superparamagnetic magnetite/IPEC particles

Hybrid magnetic composites are materials with great potential for use in biomedicine and effluent treatments, as their organic phase may be used in the adsorption/release of pollutants/drugs and their magnetic properties for separation/transport of particulate systems based on these materials. In this work we obtained magnetic composite particles made of magnetite nanoparticles dispersed in a polymeric matrix resultant from the formation of interpolyelectrolyte complexes based on chitosan and poly(sodium 4-styrenesulfonate). Non-stoichiometric positive and negatively charged interpolyelectrolyte complexes were obtained and characterized via thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffraction analysis, transmission electron microscopy, zeta potentiometry, and vibrating sample magnetometry. The samples obtained in this work showed that nanometric magnetite was incorporated to these systems and that the resultant composites were superparamagnetic. Preliminary tests showed that the composites may be used both in the sorption of cationic and anionic drugs.

Efficient prevention of nanomaterials transport in the porous media by treatment with polyelectrolytes

Contamination of soil by engineered nanomaterials (ENM) is an emergent environmental problem that urges the development of robust treatment protocols to prevent ENM transport through soil. We developed a method for efficient entrapment and retention of ENM in solid porous media of quartz sand with grain size of 300–500 μm used as a simple model of soil and studied the transport properties of multi-walled carbon nanotubes, fullerenes, silica and gold nanoparticles through the sand-packed column by UV–vis and fluorescent spectroscopy. The treatment of ENM-contaminated porous media with a mixture of oppositely charged polyelectrolytes, cationic poly(diallyldimethylammonium chloride) and anionic poly(acrylic acid) sodium salt, dissolved in NaCl solution followed by dilution in the column results in strong electrostatic interaction between the polyelectrolytes and a formation of inter-polyelectrolyte complexes (IPEC) that induce flocculation of ENM and adsorption to the surface of sand. The method demonstrates excellent ENM entrapment efficiency (>90%) and high capacity of several grams of ENM per 1 g of polyelectrolytes. The IPEC network formed after the treatment also serves as an efficient protection barrier for newly added ENM contaminants. The method is universal for various types of ENM (carbon ENM, metal and oxide nanoparticles) and equally efficient for distilled water, tap water, or lake water eluents.

Formation of core/corona nanoparticles with interpolyelectrolyte complex cores in aqueous solution: insight into chain dynamics in the complex from fluorescence quenching.

Formation of interpolyelectrolyte complexes (IPECs) of poly(methacrylic acid) (PMAA) bearing a fluorescent label (umbelliferone) at the chain end and poly[3,5-bis(trimethyl ammoniummethyl)-4-hydroxystyrene iodide]-block-poly(ethylene oxide) (QNPHOS-PEO) acting as a fluorescence quencher, was followed using a combination of scattering, calorimetry, microscopy and fluorescence spectroscopy techniques. While scattering and microscopy measurements indicated formation of spherical core/corona nanoparticles with the core of the QNPHOS/PMAA complex and the PEO corona, fluorescence measurements showed that both static and dynamic quenching efficiency were increased in the nanoparticle stability region. As the dynamic quenching rate constant remained unchanged, the quenching enhancement was caused by the increase in the local concentration of QNPHOS segments in the microenvironment of the label. This finding implies that the local dynamics of PMAA end chains affecting the interaction of the label with QNPHOS segments was independent of both PMAA and QNPHOS chain conformations.

Formation of interpolyelectrolyte complexes with controlled hydrodynamic radii in solutions

Interpolyelectrolyte complexes (IPEC) of poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) and comb-like amphiphilic polyelectrolyte poly(11-acryloyloxyundecyltrimethyl-ammonium) cation (PAUTA) were synthesized via polymerization of AUTA ionically bound to a PAMPS macromolecule. Nanoparticle dispersions with controlled hydrodynamic radii were prepared by varying molecular weight of the initial PAMPS. The morphology and sizes of IPEC dispersions were studied by atomic force microscopy (AFM). Nanoparticles dispersions stability under different salt conditions was assessed.