SEARCH · Search PubMed

Results for “Polyelectrolytes”

Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,711 records · Page 95Linked to original sources

PubMed1996

Enhancement of the polycation-mediated DNA uptake and cell transfection with Pluronic P85 block copolymer.

Polyelectrolyte complexes formed between DNA and poly(N-ethyl4-vinylpyridinium) cations were shown to effectively transfect mammalian cells [7]. This work suggests that the polycation-mediated uptake of the plasmid DNA and cell transfection are significantly enhanced when these complexes are administered simultaneously with a poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymer, Pluronic P85. The uptake studies were performed using radioactively labeled pRSV CAT plasmid on NIH 3T3, MDCK, and Jurkat cell lines. The transfection was investigated by chloramphenicol acetyltransferase assay using 3T3 cells as a model. The effects reported may be useful for the enhancement of the polycation-mediated cell transfection.

3T3 Cells↗

PubMed2002

Physical properties and in vitro transfection efficiency of gene delivery vectors based on complexes of DNA with synthetic polycations.

Biophysical properties of polycation/DNA complexes designed for gene delivery were studied with respect to the conditions of their preparation, chemical structure and molecular weight of the polycations involved. The polycations used included a variety of cationic polymers and copolymers containing primary and tertiary amino or quaternary ammonium groups. It was found that the molecular weight and the size of these polyelectrolyte complexes (PECs) increase with increasing temperature and pH of the buffer. By decreasing the molecular weight of polycations used for PEC formation, the complexes become unstable towards coagulation in aqueous solution at lower pH. The self-assembly of DNA with low-molecular-weight polycations in water provides PECs with the lowest molecular weight, smallest size and the lowest density but their stability in NaCl solutions is very poor. Despite the complexity of the multistep transfection process, a direct correlation between the transfection efficiency in vitro and the stability of the complexes in NaCl solutions and coagulation in 0.15 M NaCl solution was found. DNA complexes with polycations containing primary amino groups showed the best stability in saline solutions and also the best transfection activity. PECs formed by polycations with quaternary ammonium groups were the least resistant to destruction by the added salt and provided the lowest activity in transfection assays. The highest transfection activity was found for DNA complexes formed with a statistical copolymer containing primary and tertiary amines.

Animals↗

PubMedDate not supplied

Aliphatic ionenes as gene delivery agents: elucidation of structure-function relationship through modification of charge density and polymer length.

Polycation-based gene delivery agents are generally polydisperse populations whose properties are averaged among the different molecular weight species. Therefore, to understand the physicochemical properties of polycations and their relationships to cellular gene transfer, one needs to control the molecular weight of the polymer as well as its cationic charge density. To investigate the structure-function correlation of polycations with respect to the degree of polymerization (DP) and charge density, a series of model materials based on aliphatic ionenes was synthesized and fractionated into distinct molecular weight fractions with DP range from 14 to 32. The aliphatic ionene fractions and their polyelectrolyte complexes (PEC) with DNA were studied using physicochemical and biological methods. Ionene polymers were shown to possess low cytotoxicity (minimal viability of the P388D1 murine macrophage cells 80%). DP and charge density of the ionenes were shown to be the factors of effective control of PEC dissociation in water-salt solutions, with a diminished role of charge density upon lengthening the ionene chain. These polymer characteristics were also important for DNA-ionene PEC resistivity to DNase activity and the ability of ionenes to serve as gene delivery vectors in vitro and exhibited good correlation with the results of salt-induced dissociation of PEC. These data may be useful for developing correlations and mathematical models to predict synthetic gene delivery vector efficiency.

Animals↗

PubMedDate not supplied

Effect of albumin and polyanion on the structure of DNA complexes with polycation containing hydrophilic nonionic block.

Self-assembling systems based on ionic complexes of DNA with block copolymer of N-(2-hydroxypropyl)methacrylamide with 2-(trimethylammonio)ethyl methacrylate were studied as systems suitable for gene delivery. In this study, the influence of albumin and polyanion on parameters of the DNA polyelectrolyte complexes in aqueous solutions was investigated. Static and dynamic light-scattering methods were used as a main tool for characterizing these interactions. It was found that albumin is not able to release free DNA, but it can rather bind to the complexes forming ternary DNA-polycation-albumin complexes with increased hydrodynamic radii of about 10 nm. Polyanion tested, sodium poly(styrenesulfonate), was able to release free DNA in the presence of a low-molecular-weight electrolyte. In the absence of a low-molecular-weight electrolyte, only formation of ternary complexes and no DNA release was observed. The in vivo biodistribution analysis of DNA complexes showed no effect of the presence of hydrophilic nonionic poly(HPMA) on the circulatory time or organ distribution. The interaction of DNA complexes with albumin and other plasma proteins was suggested to be a major reason for the short circulatory times.

Animals↗

PubMed2004

Coadsorption of sodium dodecyl sulfate and a polyanion onto poly(ethylenimine) in multilayered thin films.

Mixed surfactant-polyelectrolyte multilayer films were fabricated by both ionic self-assembly and spin assembly. A polycation [PEI = poly(ethylenimine)] was deposited from a dilute solution, while a polyanion (PAZO = poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt]) was deposited from a mixture containing a fixed concentration of polyanion and various concentrations of the anionic surfactant sodium dodecyl sulfate (SDS). Coadsorption of SDS and PAZO onto PEI layers was observed using both deposition methods and attributed to strong PEI-SDS interactions and entropic factors. Increasing the concentration of SDS resulted in films containing progressively less adsorbed PAZO. No further reduction in the amount of adsorbed PAZO was observed above the SDS critical micelle concentration. We attribute the film growth behavior to a fast adsorption of SDS onto PEI, followed by a slower adsorption of PAZO onto the remaining unoccupied binding sites. We observe that SDS interpenetrates throughout the PAZO and PEI layers, increasing the surface hydrophobicity of both. We observed similar behavior for both ionically self-assembled and spin-assembled systems.

Adsorption↗

PubMed1986

The long-term culture of encapsulated pancreatic islets.

A new encapsulation technique, the formation of a polyelectrolyte complex membrane from sodium cellulose sulphate and a polycationic solution (polydimethyldiallylammoniumchloride) can be used for culturing pancreatic islets. After 5 weeks of culture, such encapsulated islets were morphologically well preserved, and parameters of cell viability and functionality such as DNA content and DNA synthesis, insulin content and stimulated insulin release were not different between the encapsulated and non-encapsulated control islets. A lower insulin secretion into the medium of the encapsulated islets during the first 3 weeks of culture can probably be explained by the capsule diameter (4-5 mm) and should be improved using microcapsules with a diameter of less than 1 mm.

1-Methyl-3-isobutylxanthine↗

PubMed1983

Polyanions and glucose as osmotic agents in simulated peritoneal dialysis.

Peritoneal dialysis solutions contain glucose as an osmotic agent to obtain ultrafiltration. Due to rapid absorption, glucose does not sustain high ultrafiltration during long exchanges. Nonabsorbable polyanions might be effective as osmotic agents when suspended in electrolyte solution. Concentrations of freely diffusible ions should be in Gibbs-Donnan equilibrium with plasma electrolytes. The ideal proportion of diffusable to polymerbound cation concentrations is unknown. To obtain concentrations of free ions in equilibrium with plasma, it is assumed that the polymer solution dialyzed against a polyelectrolyte solution of the desired composition (with hydraulic pressure higher on the polymer side) will approach the same thermodynamic activity as the electrolyte solution. Subsequently, if transmembrane pressure is released, osmotic ultrafiltration will occur in proportion to the hydrostatic pressure applied during polymer solution preparation. Polyacrylate solution so prepared was compared with a commercial dextrose dialysis solution in an in vitro simulation of peritoneal dialysis. With dwell times up to 24 h, sustained ultrafiltration with polymer was observed, whereas, with dextrose, ultrafiltration ceased after 8 h. Concentrations of diffusible bivalent cations in polyacrylate were lower than intended due to avid polymer complexing; however, dextran sulfate solutions were developed to contain desired concentrations of diffusible electrolytes. The conclusion is that some polymer solutions might be useful in clinical settings when high sustained ultrafiltration is needed.

Acrylic Resins↗

PubMed1988

[Interaction of amino acyl-tRNA-synthetases from the rabbit liver with RNA and polyanions].

The interaction of aminoacyl-tRNA synthetase with RNA and polyanions was studied. The inhibition of the enzymes by polyU, polyI and heparin was demonstrated. It was found that this interaction is of limited specificity and is typical of single-stranded RNAs which possess no orderly secondary structure as well as of other polyanions possessing similar polyelectrolytic properties. Data from kinetic analysis and lysyl-tRNA synthetase modification by pyridoxal phosphate are suggestive of participation of the tRNA binding site in the enzyme interaction with polyanions.

Amino Acyl-tRNA Synthetases↗

PubMed1996

A comparative study of the high-frequency dielectric properties of poly (alpha-glutamate) and poly (gamma-glutamate) aqueous solutions.

The dielectric properties of poly(alpha-glutamic acid) and poly(gamma-glutamic acid) aqueous solutions in the fully ionized state have been investigated in the frequency range from 1 MHz to 1 GHz by means of frequency-domain dielectric spectroscopy measurements. In this frequency range, micro-Brownian dynamics and internal motion of side-chain polar groups give rise to nonexponential relaxation processes resulting in an intermediate dielectric relaxation between that due to the counterion atmosphere polarization and that due to the orientational polarization of the water molecules. In this work, we study the influence of the polymer concentration in the dilute--semidilute regime on the dielectric parameters, i.e., the dielectric increment delta epsilon and the relaxation time tau, and discuss their relevance in the light of some scaling pictures recently proposed by Dobrynin, Colby, and Rubinstein to describe the unentangled regime of flexible polyelectrolyte solutions.

Chemical Phenomena↗

PubMed1997

Energetics of drug-DNA interactions.

Understanding the thermodynamics of drug binding to DNA is of both practical and fundamental interest. The practical interest lies in the contribution that thermodynamics can make to the rational design process for the development of new DNA targeted drugs. Thermodynamics offer key insights into the molecular forces that drive complex formation that cannot be obtained by structural or computational studies alone. The fundamental interest in these interactions lies in what they can reveal about the general problems of parsing and predicting ligand binding free energies. For these problems, drug-DNA interactions offer several distinct advantages, among them being that the structures of many drug-DNA complexes are known at high resolution and that such structures reveal that in many cases the drug acts as a rigid body, with little conformational change upon binding. Complete thermodynamic profiles (delta G, delta H, delta S, delta Cp) for numerous drug-DNA interactions have been obtained, with the help of high-sensitivity microcalorimetry. The purpose of this article is to offer a perspective on the interpretation of these thermodynamics parameters, and in particular how they might be correlated with known structural features. Obligatory conformational changes in the DNA to accommodate intercalators and the loss of translational and rotational freedom upon complex formation both present unfavorable free energy barriers for binding. Such barriers must be overcome by favorable free energy contributions from the hydrophobic transfer of ligand from solution into the binding site, polyelectrolyte contributions from coupled ion release, and molecular interactions (hydrogen and ionic bonds, van der Waals interactions) that form within the binding site. Theoretical and semiempirical tools that allow estimates of these contributions to be made will be discussed, and their use in dissecting experimental data illustrated. This process, even at the current level of approximation, can shed considerable light on the drug-DNA binding process.

Base Sequence↗

PubMed1999

Binding of proteins to copolymers of varying hydrophobicity.

Hydrophobic interactions between proteins and amphiphilic polyelectrolytes were studied by frontal analysis continuous capillary electrophoresis (Gao et al., Analytical Chemistry, 1997, Vol. 69, pp. 2945-2951). Binding isotherms were obtained for beta-lactoglobulin and for bovine serum albumin interacting with a series of alternating copolymers of maleic acid and alkyl-vinyl ethers of varying hydrophobicity. Although binding between proteins and copolymers increases with increasing alkyl chain length, a minimum alkyl chain length of 3-4 methylenes is required for significant hydrophobic interactions to occur. These copolymers, like other polyamphiphiles, can form intrapolymer micelles, and the extent of such micellization decreases with increasing degree of carboxylate ionization. Binding results obtained at different pHs suggest that competition exists between intrapolymer micelle formation and protein-polymer hydrophobic interactions.

Animals↗

PubMed1999

Divalent cations and the electrostatic potential around DNA: Monte Carlo and Poisson-Boltzmann calculations.

The predictions of counterion condensation theory for divalent ions were tested by comparison with the results of Monte Carlo calculations on an all-atom model of DNA. Monovalent-divalent competition at the polyelectrolyte surface was investigated by varying the partial molar volume of divalent ions. To assess the viability of using Poisson-Boltzmann (PB) calculations for determining divalent ion concentrations at DNA surfaces, Monte Carlo (MC) calculations were compared with PB calculations using different models of the dielectric continuum. It was determined that, while standard PB calculations of divalent ion surface densities are about 25-30% below those predicted by MC techniques, and somewhat larger than errors previously determined for monovalent ions, errors due to the use of the mean-field approximation of PB theory are smaller than those arising from common assumptions regarding the dielectric continuum.

Animals↗

PubMed1999

Study of the interactions of D- and L-polylysine enantiomers withpectate in aqueous solutions.

The interaction between D- and L-enantiomers of polylysine and potassium pectate was studied by means of CD, microcalorimetry, and osmometry. Upon binding with pectate, only poly(L-lysine) undergoes a coil to alpha-helix transition, while poly(D-lysine) remains in the disordered state. This suggest that the energetics of the interaction is influenced by stereochemical constraints besides electrostatic forces. Experimental findings from microcalorimetry suggest that a contribution to the overall enthalpy of binding comes from the polysaccharidic moiety. Stoichiometry of the macromolecular complexes studied by osmometry gives a polylysine:pectate ratio of 3:1, in agreement with the respective degree of polymerization of the two polyelectrolytes.

Calorimetry↗

PubMed1999

Thermodynamics of stabilization of RNA pseudoknots by cobalt(III) hexaammine.

Equilibrium unfolding (folding) studies reveal that the autoregulatory RNA pseudoknots derived from the bacteriophage T2 and T4 gene 32 mRNAs exhibit significant stabilization by increasing concentrations of divalent metal ions in solution. In this report, the apparent affinities of exchange inert trivalent Co(NH(3))(3+)(6) have been determined, relative to divalent Mg(2+), for the folded, partially folded (K(f)), and fully unfolded (K(u)) conformations of these molecules. A general nonspecific, delocalized ion binding model was developed and applied to the analysis of the metal ion concentration dependence of individual two-state unfolding transitions. Trivalent Co(NH(3))(3+)(6) was found to associate with the fully folded and partially unfolded pseudoknotted forms of these RNAs with a K(f) of 5-8 x 10(4) M(-1) in a background of 0.10 M K(+), or 3- to 5-fold larger than the K(f) obtained for two model RNA hairpins and hairpin unfolding intermediates, and approximately 40-50-fold larger than K(f) for Mg(2+). The magnitude of K(f) was found to be strongly dependent on the monovalent salt concentration in a manner qualitatively consistent with polyelectrolyte theory, with K(f) reaching 1.2 x 10(5) M(-1) in 50 mM K(+). Two RNA hairpins were found to have affinities for Co(NH(3))(3+)(6) and Ru(NH(3))(3+)(6) of 1-2 x10(4) M(-1), or approximately 15-fold larger than the K(f) of approximately 1000 M(-1) observed for Mg(2+). Additionally, the K(u) of 4,800 M(-1) for the trivalent ligands is approximately 8-fold larger than the K(u) of 600 M(-1) observed for Mg(2+). These findings suggest that the T2 and T4 gene 32 mRNA pseudoknots possess a site(s) for Mg(2+) and Co(NH(3))(3+)(6) binding of significantly higher affinity than a "duplexlike" delocalized ion binding site that is strongly linked to the thermodynamic stability of these molecules. Imino proton perturbation nmr spectroscopy suggests that this site(s) lies near the base of the pseudoknot stem S2, near a patch of high negative electrostatic potential associated with the region where the single loop L1 adenosine crosses the major groove of stem S2.

Base Sequence↗

PubMed1998

Ionic interactions in nanofiltration of beta casein peptides

Nanofiltration (NF) membrane technology shows interesting potentials for separating organic components on the basis of solute charge and size in the range of 300-1000 g mol-1. Separation properties of two inorganic NF membranes were studied with a set of 10 small peptides (molecular mass range: 300-900 g mol-1; 3 < pI < 10) contained in a well-characterized tryptic beta casein hydrolysate. Peptides transmission strongly depended on ionic interactions in the system. Physicochemical conditions such as ionic strength and especially pH were crucial to the separation, because the membrane and peptides showed amphoteric properties. Thus, the three categories of peptides (acid, basic, neutral) were separated according to their pI because of presumed concentration gradients of charged peptides at the membrane: positive for basic peptides and negative for acid peptides. At optimum pH 8 this led to high transmissions of basic peptides (even over 100%), intermediate transmissions for neutral peptides, and low transmissions for acid peptides. The addition of multicharged cationic and anionic species in the hydrolysate induced a markedly enhanced selectivity when the polyelectrolyte was a membrane coion and a complete reversion of selectivity when it was a membrane counterion. Copyright 1998 John Wiley & Sons, Inc.

Journal Article↗

PubMed1998

Control and measurement of permeability for design of microcapsule cell delivery system.

Transplantation of immunoisolated islets of Langerhans has been proposed as a promising approach to treating insulin-dependent diabetes mellitus. Recently, a cell delivery system based on a multicomponent microcapsule has been designed for the immunoisolation of insulin-secreting pancreatic islets. The capsule, formed by polyelectrolyte complexation of sodium alginate and cellulose sulfate with poly(methylene-co-guanidine), markedly has improved mechanical strength compared with the widely used alginate/poly(L-lysine) capsules. It also provides a flexibility for readily adjusting membrane thickness and capsule size, and, more important, the membrane permeability can be altered over a wide range of molecular sizes. To rigorously test the capsule diffusion properties, we have improved capsule permeability measurement by using two complementary methods: (1) size exclusion chromatography with dextran standards; and (2) newly developed methodology for assessing permeability to a series of biologically relevant proteins. Viability and function of rat pancreatic islets enclosed in the capsules with different permeability were tested in vitro. The insulin secretion of encapsulated islets was well preserved even though slightly delayed in comparison with a control group of free islets. We believe that the unique features of this encapsulation system together with the precise characterization of its physical parameters will enable us to find the optimal range of capsule permeability for in vitro and in vivo survival and function of encapsulated pancreatic islets.

Alginates↗

PubMedDate not supplied

Binding of Escherichia coli LexA repressor to the RecA operator.

Equilibrium binding of Escherichia coli LexA repressor to the recA operator was studied by the polyacrylamide gel mobility shift assay as a function of solution conditions. In the presence of NaCl at 20 degrees C, there was a significant salt dependence in binding to the recA operator, typical for protein-nucleic acid interactions with some electrostatic contribution to the binding free energy. In preliminary experiments in which the anion of the Na+ salt was changed from chloride to fluoride, little change was found with anion identity. This indicates that the salt effect on the binding interaction arises solely from the polyelectrolyte effect, not from anion binding or release by the protein upon complex formation. Increasing the temperature to 37 degrees C changed the binding affinity for complex formation at any given salt concentration and resulted in a change in the sensitivity of complex formation to NaCl concentration. Quantitative analysis of the data to obtain equilibrium binding constants is discussed.

Anions↗

PubMed1998

Glycosaminoglycan-protein interactions: definition of consensus sites in glycosaminoglycan binding proteins.

Although interactions of proteins with glycosaminoglycans (GAGs), such as heparin and heparan sulphate, are of great biological importance, structural requirements for protein-GAG binding have not been well-characterised. Ionic interactions are important in promoting protein-GAG binding. Polyelectrolyte theory suggests that much of the free energy of binding comes from entropically favourable release of cations from GAG chains. Despite their identical charges, arginine residues bind more tightly to GAGs than lysine residues. The spacing of these residues may determine protein-GAG affinity and specificity. Consensus sequences such as XBBBXXBX, XBBXBX and a critical 20 A spacing of basic residues are found in some protein sites that bind GAG. A new consensus sequence TXXBXXTBXXXTBB is described, where turns bring basic interacting amino acid residues into proximity. Clearly, protein-GAG interactions play a prominent role in cell-cell interaction and cell growth. Pathogens including virus particles might target GAG-binding sites in envelope proteins leading to infection.

Amino Acid Sequence↗