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Formation of polyelectrolyte multilayers on fibres: influence on wettability and fibre/fibre interaction.

Polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulfonate (PSS) have been used to build-up polyelectrolyte multilayers (PEMs) on chemical soft wood fibres and on SiO2 at various electrolyte concentrations. Adsorption onto SiO2 was studied using a stagnation point adsorption reflectometer (SPAR), and the adsorbed amount of PDADMAC and PSS on the fibres was determined using nitrogen analysis and Schöniger burning, respectively. The adsorption onto the two substrates was then compared. Paper testing showed that the tensile index (TI) increased by about 90% when 11 layers had been adsorbed, and that there was a correlation between the adsorbed amount and the increase in TI. It was also shown that the particular polymer present in the outermost layer significantly influenced the TI, and that PDADMAC produced a higher TI. A correlation between the adsorbed amount and the TI was also found. Individual fibres were partly treated with a PEM and analysed using a dynamic contact angle analyser (DCA) and environmental scanning electron microscopy (ESEM).

Journal Article↗

Adsorption of novel thermosensitive graft-copolymers: Core-shell particles prepared by polyelectrolyte multilayer self-assembly.

The adsorption properties of thermosensitive graft-copolymers are investigated with the aim of developing self-assembled multilayers from these copolymers. The copolymers consist of a thermoreversible main chain of poly(N-isopropylacrylamid) and a weak polyelectrolyte, poly(2-vinylpyridine), as grafted side chains. Zeta-potential, single particle light scattering and adsorption isotherms monitor the adsorption of the thermoreversible copolymers to precoated colloidal particles. The results show a smaller surface coverage for a larger density of grafted chains. The surface coverage is discussed in terms of surface charge density in the adsorbed monolayer. Taking into account the monolayer adsorption properties, conditions are developed for the multilayer formation from these copolymers. A low pH provides a sufficient charge density of the grafted chains to achieve a surface charge reversal of the colloids upon adsorption. The charge reversal after each adsorbed layer is monitored by zeta-potential and the increase of the thickness is determined by light scattering. Stable and reproducible multilayers are obtained. The results imply that the conformation of the thermosensitive component in multilayers depends strongly on the grafting density, where the polymer with a higher grafting density adsorbs in a flat conformation while that with a lower grafting density adsorbs with more loops.

Journal Article↗

Phase behavior of gemini surfactant hexylene-1,6-bis(dodecyldimethylammonium bromide) and polyelectrolyte NaPAA.

The phase behavior of aqueous mixtures of gemini surfactant hexylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) and oppositely charged polyelectrolyte sodium polyacrylate (NaPAA) has been studied experimentally. Compared to the mixtures of the traditional surfactant dodecyltrimethylammonium bromide (DTAB) and NaPAA, the gel phase region in the 12-6-12/NaPAA solution is larger. Element analysis reveals that NaPAA in the gel phase tends to replace the counterions of surfactant micelle and to release its own counterions. Spherical aggregates are observed in either top or bottom gel phase as detected by transmission electron microscopy. The addition of sodium bromide (NaBr) leads to a decrease in the gel phase region and the occurrence of a new cream phase.

Journal Article↗

Interactions between gemini surfactant alkanediyl-alpha,omega-bis(dodecyldimethylammonium bromide) and polyelectrolyte NaPAA.

Interactions between cationic gemini surfactant alkanediyl-alpha,omega-bis(dodecyldimethylammonium bromide) (12-n-12, n=3,4,6) and oppositely charged polyelectrolyte sodium polyacrylate (NaPAA) in aqueous solution have been investigated by measuring fluorescence, conductivity, UV-vis transmittance, dynamic lighting scattering, and transmission electron microscopy. Micelle-like structure and 12-n-12/NaPAA complex are observed to form due to the electrostatic and hydrophobic interactions, and the effective diameter of the complex reduces with increasing 12-n-12 concentration. The microstructures of 12-n-12/NaPAA solution determined from fluorescence and electron microscopy measurements are in good agreement. The spacer length is found to play an important role in the interactions of 12-n-12 with NaPAA.

Journal Article↗

Multilayered polyelectrolyte films promote the direct and localized delivery of DNA to cells.

Multilayered polyelectrolyte films fabricated from plasmid DNA and a hydrolytically degradable synthetic polycation can be used to direct the localized transfection of cells without the aid of a secondary transfection agent. Multilayered assemblies 100 nm thick consisting of alternating layers of synthetic polymer and plasmid DNA encoding for enhanced green fluorescent protein (EGFP) were deposited on quartz substrates using a layer-by-layer fabrication procedure. The placement of film-coated slides in contact with COS-7 cells growing in serum-containing culture medium resulted in gene expression in cells localized under the film-coated portion of the slides. The average percentage of cells expressing EGFP relative to the total number of cells ranged from 4.6% to 37.9%, with an average of 18.6%+/-8.2%, as determined by fluorescence microscopy. In addition to providing a mechanism for the immobilization of DNA at the cell/surface interface, a preliminary analysis of film topography by atomic force microscopy (AFM) demonstrated that polymer /DNA films undergo significant structural rearrangements upon incubation to present surface bound condensed plasmid DNA nanoparticles. These data suggest that the presence of the cationic polymer in these materials may also contribute to the internalization and expression of plasmid. The materials and design principles reported here present an attractive framework for the local or non-invasive delivery of DNA from the surfaces of implantable materials or biomedical devices.

Animals↗

One-step preparation of polyelectrolyte-coated PLGA microparticles and their functionalization with model ligands.

This work aimed at the development of a novel surfactant-free, one-step process for the concomitant formation of poly(lactide-co-glycolide) (PLGA) microparticles (MP) and surface coating with the polyelectrolyte chitosan, which is suitable for subsequent covalent conjugation of bioactive ligands. The technology is based on solvent extraction from an O/W-dispersion using a static micromixer. Surface coating occurred through interaction of the negatively charged, nascent PLGA MP with the polycationic chitosan, which was dissolved in the aqueous extraction fluid. Particles of 1-10 mum in diameter were produced with excellent reproducibility. The chitosan-coated PLGA MP were spherical and showed a smooth surface without pores, as demonstrated by scanning electron microscopy (SEM). The chitosan coatings were characterized by zeta potential measurements and X-ray photoelectron spectroscopy (XPS). The functional amino groups of chitosan were used to conjugate two model ligands to the coating, i.e. fluorescamine and NHS-PEG-biotin. The presence of the conjugated ligands was revealed by confocal laser scanning microscopy (CLSM) and fluorescence activated cell sorting (FACS). Evidence for biotinylation was demonstrated through binding of fluorescently labelled streptavidin. The developed platform technology is straightforward and flexible. Future studies will focus on the design of microparticulate carriers with bioactive surfaces, e.g. as antigen delivery systems.

Biocompatible Materials↗

Preparation of polyelectrolytes for wastewater treatment.

Liquid-phase polymerisation of acrylamide-acrylic acid to form polyelectrolytes used in wastewater cleaning was examined using accelerated electron beam and microwave irradiation methods. Polymerisation was carried out in aqueous solutions at temperatures approximately 60 degrees C. Monomers total concentration was established at 40% (36% acrylamide and 4% acrylic acid). Only using the features of simultaneous radiation-induction and microwave heating can result in the formation of linear polymer chains with good water solubility and low residual monomer concentration. The flocculation capacity of the obtained polymers was tested using two wastewaters, one sampled from a slaughterhouse and the other from a vegetable oil plant. Quality indicators such as total suspended matters (TSM), chemical oxygen demand (COD), biological oxygen demand (BOD) and fat, oils and grease (FOG) were measured before and after the treatment with polymeric flocculants and compared with the results obtained in classical treatment with Al(2)(SO(4))(3). It was found that the combined treatment with polymers and Al(2)(SO(4))(3) increases the degree of purification of both wastewaters up to 99%.

Acrylamide↗

Topological alterations in human spermatozoa associated with the polyelectrolytic effect of RISUG.

A new method of male contraception has been developed which results in long-term infertility and has the potential advantage of being reversible. The contraceptive, given the name RISUG (an acronym for Reversible Inhibition of Sperm Under Guidance) is a polyelectrolytic compound and when injected into the lumen of the vas deferens, induces a surface charge imbalance on the sperm membrane system leading to its destabilization. In the present study, morphological and topological alterations in human spermatozoa induced by RISUG have been investigated using atomic force microscopy (AFM). Complete disintegration of the plasma membrane with subsequent rupture and dispersion of the acrosomal contents is observed on treatment with RISUG in vitro. Considerable damage to the midpiece region with significant clustering of the mitochondria and its fusion with the head region is also observed. These observations are in agreement with the significant increase in the volume of RISUG-treated sperm-head region. Topological alterations in the flagellar and midpiece region of RISUG-treated spermatozoa have also been studied.

Acrosome↗

Nonviral gene delivery from nonwoven fibrous scaffolds fabricated by interfacial complexation of polyelectrolytes.

We investigated a novel nonwoven fibrous scaffold as a vehicle for delivery of DNA. Fibers were formed by polyelectrolyte complexation of water-soluble chitin and alginate, and PEI-DNA nanoparticles were encapsulated during the fiber drawing process. Nanoparticles released from the fibers over time retained their bioactivity and successfully transfected cells seeded on the scaffold in a sustained manner. Transgene expression in HEK293 cells and human dermal fibroblasts seeded on the transfecting scaffolds was significant even after 2 weeks of culture compared to 3-day expression in two-dimensional controls. Fibroblasts seeded on scaffolds containing DNA encoding basic fibroblast growth factor (bFGF) demonstrated prolonged secretion of bFGF at levels significantly higher than baseline. This work establishes the potential of this fibrous scaffold as a matrix capable of delivering genes to direct and support cellular development in tissue engineering.

Alginates↗

Structural forces reflecting polyelectrolyte organization from bulk solutions and within surface complexes.

The interactions between two macroscopic surfaces approaching one another underlies many of the phenomena observed in Colloid and Interface science. In Russia this gave rise to the branch of colloid science now referred to as Surface Forces. Important discoveries, such as the molecular organization of solvent molecules at an interface, have been unveiled by surface force measurements. More recently, forces and structures at macromolecular length scales have been uncovered. In particular, oscillatory force profiles have been detected from aqueous solutions containing polyelectrolytes. The force-structure relationship can reflect organization in the bulk solution or the internal structure of the adsorbed layer. Using a range of surface force techniques, combined with X-ray and neutron scattering results, we review the main features of these fascinating systems and provide an overview of how they relate to other systems such as micellar solutions, polymer-surfactant complexes and simple solvents.

Journal Article↗

PROPERTIES OF DOUBLE-STRANDED DNA AS A POLYELECTROLYTE.

The stability of the structure of double-stranded DNA in the salt-free solution is discussed on the basis of the polyelectrolyte theory. Assuming that DNA is an infinitely long rod, and the formation of double strands is divided into combining process and folding process, the free energy changes required in these processes are calculated by the use of the exact solutions of two-dimensional Poisson-Boltzmann equation for the one rod and the two rod systems.By strong depression of electrostatic interaction due to counter-ion condensation phenomena, the free energy change is remarkably decreased so that the double-stranded structure of DNA can be stabilized by energy of hydrogen bonds between base pairs. The increase of the activity coefficient of a counterion upon heat denaturation of DNA is also explained.

Biophysical Phenomena↗

Force balances in systems of cylindrical polyelectrolytes.

A detailed analysis is made of the model system of two parallel cylindrical polyelectrolytes which contain ionizable groups on their surfaces and are immersed in an ionic bathing medium. The interaction between the cylinders is examined by considering the interplay between repulsive electrostatic forces and attractive forces of electrodynamic origin. The repulsive force arises from the screened coulomb interaction between the surface charge distributions on the cylinders and has been treated by developing a solution to the linearized Poisson-Boltzmann equation. The boundary condition at the cylinder surfaces is determined as a self-consistent functional of the potential, with the input consisting of the density of ionizable groups and their dissociation constants. It is suggested that a reasonably accurate representation for the form of the attractive force can be obtained by performing a pairwise summation of the individual interatomic forces. A quantitative estimate is obtained using a Hamaker constant chosen on the basis of rigorous calculations on simpler systems. It is found that a balance exists between these repulsive and attractive forces at separations in good agreement with those observed in arrays of tobacco mosaic virus and in the A band myosin lattice in striated muscle. The behavior of the balance point as a function of the pH and ionic strength of the bathing medium closely parallels that seen experimentally.

Electrolytes↗

Donnan potential measurements in extended hexagonal polyelectrolyte gels such as muscle.

In this paper we reconsider the theoretical and practical aspects of using KCl-filled microelectrodes in extended polyelectrolyte gels such as muscle to measure Donnan potentials, and then calculate protein fixed-charge concentrations. An analytical calculation of the electrical potential function between muscle filaments shows that whether the microelectrode averages the ionic concentration or the local potentials the results are indistinguishable in the practical regime. After consideration of this and other possible sources of error, we conclude that the charge-concentrations measurements that have appeared in the literature are legitimate.

Animals↗

Membrane solubilization by a hydrophobic polyelectrolyte: surface activity and membrane binding.

We have previously observed that the hydrophobic polyelectrolyte poly(2-ethylacrylic acid) solubilizes lipid membranes in a pH-dependent manner, and we have exploited this phenomenon to prepare lipid vesicles that release their contents in response to pH, light, or glucose (Thomas, J. L., and D. A. Tirrell. Acc. Chem. Res. 25:336-342, 1992). The physical basis for the interaction between poly(2-ethylacrylic acid) and lipid membranes has been explored using surface tensiometry and fluorimetry. Varying the polymer concentration results in changes in surface activity and membrane binding that correlate with shifts in the critical pH for membrane solubilization. Furthermore, the binding affinity is reduced as the amount of bound polymer increases. These results are consistent with a hydrophobically driven micellization process, similar to those observed with apolipoproteins, melittin, and other amphiphilic alpha-helix-based polypeptides. The absence of specific secondary structure in the synthetic polymer suggests that amphiphilicity, rather than structure, is the most important factor in membrane micellization by macromolecules.

Acrylates↗

Binding of ionic ligands to polyelectrolytes.

Ionic ligands can bind to polyelectrolytes such as DNA or charged polysaccharides. We develop a Poisson-Boltzmann treatment to compute binding constants as a function of ligand charge and salt concentration in the limit of low ligand concentration. For flexible chain ligands, such as oligopeptides, we treat their conformations using lattice statistics. The theory predicts the salt dependence and binding free energies, of Mg(2+) ions to polynucleotides, of hexamine cobalt(III) to calf thymus DNA, of polyamines to T7 DNA, of oligolysines to poly(U) and poly(a), and of tripeptides to heparin, a charged polysaccharide. One parameter is required to obtain absolute binding constants, the distance of closest separation of the ligand to the polyion. Some, but not all, of the binding entropies and enthalpies are also predicted accurately by the model.

Animals↗

Precipitation of DNA by polyamines: a polyelectrolyte behavior.

Conditions of double-stranded DNA precipitation by the polyamines spermidine and spermine have been determined experimentally and compared to theoretical predictions. The influence of the concentrations of DNA and added monovalent salt, and of the DNA length has been investigated in a systematic manner. Three regimes of DNA concentrations are observed. We clarify the dependence of these regimes on the monovalent salt concentration and on the DNA length. Our observations make possible a rationalization of the experimental results reported in the literature. A comparison of the precipitation conditions of different kinds of polyelectrolytes suggests a general process. Our experimental data are compared to the "ion-bridging" model based on short-range electrostatic attractions. By starting from the spinodal equation, predicted by this model, and using the limiting form of Manning's fractions of condensed counterions, analytical expressions of the precipitation conditions have been found in the three regimes. Experimental and theoretical results are in good agreement.

Animals↗

Chitosan N-sulfate. A water-soluble polyelectrolyte.

Chitosans having degrees of acetylation (da) of 0.04, 0.10, and 0.22, respectively, were N-sulfated under a variety of reaction conditions. The derivatives obtained ranged in degree of sulfation (ds) from 0.4 to 0.86 (+/-0.05). All were soluble in water, and the rheological properties of their solutions varied markedly with da and ds values. Both ionic strength and pH had an effect on their solubility properties, and also on interactions that they exhibited with O-(carboxymethyl)cellulose, xanthan gum, and heparin. Being compatible with other polyelectrolytes such as these, the chitosan derivatives may be useful in some aqueous formulations.

Biopolymers↗

Modulation of airway responsiveness by anionic and cationic polyelectrolyte substances.

To elucidate the effects of anionic and cationic polyelectrolyte substance on bronchoconstriction, we examined the serial changes in respiratory resistance (Rrs) in ovalbumin-sensitized guinea pigs after antigen exposure with or without pre-inhalation of low-molecular-weight heparin, poly-L-glutamic acid, poly-L-lysine and dextran, and with or without oral intake of dalteparin. Both immediate and late responses after antigen exposure were significantly decreased after pretreatment with inhaled low-molecular-weight heparin and poly-L-glutamic acid compared with saline alone. The late response was significantly decreased after pretreatment with oral dalteparin. Both low-molecular-weight heparin and poly-L-glutamic acid significantly decreased the airway response to methacholine in sensitized guinea pigs. In sensitized guinea pigs, the airway response to methacholine was significantly increased after pretreatment with inhaled poly-L-lysine. Pretreatment with inhaled low-molecular-weight heparin before poly-L-lysine exposure significantly suppressed the airway hyperresponsiveness after inhaled poly-L-lysine. These findings indicated that the "cationic-anionic interaction" plays an important role in airway responsiveness.

Airway Resistance↗