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PubMed2004

Secondary structure analysis of proteins embedded in spherical polyelectrolyte brushes by FT-IR spectroscopy.

The adsorption of bovine serum albumin (BSA), bovine beta-lactoglobulin, and bovine pancreatic ribonuclease A onto spherical polyelectrolyte brushes (SPB) is reported. The SPB consist of narrowly distributed poly(styrene) core particles (diameter approximately 100 nm) onto which linear chains of anionic polyelectrolytes are grafted. The polyelectrolyte shell consists of either the weak polyelectrolyte poly(acrylic acid) or the strong polyacid poly(styrenesulfonate). The SPB particles are dispersed in H(2)O at room temperature. The secondary structure of the proteins was investigated by Fourier transform infrared spectroscopy in transmission mode before and during adsorption to these colloidal brushes. The alpha-helix and beta-sheet content of the proteins was nearly fully retained in the adsorbed state for all systems. Only in the case of BSA interacting with poly(styrenesulfonic) brushes could a slight loss of alpha-helix structure be observed. As the interaction of SPB and proteins can be controlled by the ionic strength in the buffer, additional experiments were performed to release the adsorbed protein. The amount of released protein was quantified and was found to be strongly dependent on the kind of protein and brush used. The secondary structure of the released proteins could be analyzed as well. An almost full preservation of secondary structure was found. This demonstrates that SPB are well-suited to immobilize proteins. The SPB can be charged and decharged under retention of the secondary structure of the biomolecules.

Animals↗
PubMed1999

The polyelectrolyte behavior of actin filaments: a 25Mg NMR study.

Under physiological conditions, filamentous actin (F-actin) is a polyanionic protein filament. Key features of the behavior of F-actin are shared with other well-characterized polyelectrolytes, in particular, duplex DNA. For example, the bundle formation of F-actin by polyvalent cations, including divalent metal ions such as Mg2+, has been proposed to be a natural consequence of the polyelectrolyte nature of actin filaments [Tang and Janmey (1996) J. Biol. Chem. 271, 8556-8563]. This recently proposed model also suggests that weak interactions between F-actin and Mg2+ ions reflect a nonspecific trapping of counterions in the electric field surrounding F-actin due to its polyelectrolyte nature. To test this hypothesis, we have performed 25Mg NMR measurements in F-actin solutions. Based on the NMR data, we estimate that the rotational correlation times of Mg2+ are independent of the overall rotational dynamics of the actin filaments. Moreover, competitive binding experiments demonstrate a facile displacement of F-actin-bound Mg2+ by Co(NH3)63+. At higher Co(NH3)63+ concentrations, a fraction of the magnesium ions are trapped as actin filaments aggregate. ATP also competes effectively with actin filaments for binding to Mg2+. These results support the hypothesis that magnesium ions bind loosely and nonspecifically to actin filaments, and thus show a behavior typical of counterions in polyelectrolyte solutions. The observed features mimic to some extent the well-documented behavior of counterions in DNA solutions.

Actin Cytoskeleton↗
PubMed2006

Polyelectrolyte multilayer films as substrates for photoreceptor cells.

Reconstruction of extracellular matrix substrates for delivery of functional photoreceptors is crucial in pathologies such as retinal degeneration and age-related macular degeneration. In this study, we assembled polyelectrolyte films using the layer-by-layer deposition method. The buildup of three different films composed of poly(L-lysine)/chondroitin sulfate (PLL/CSA), poly(L-lysine)/poly(styrenesulfonate) (PLL/PSS), or poly(L-lysine)/hyaluronic acid (PLL/HA) was followed by means of quartz crystal microbalance measurements, optical waveguide light mode spectroscopy, confocal microscopy, and atomic force microscopy. The exponential growth regime and the diffusion of PLL chains from the bulk through the PLL/CSA, PLL/PSS, and PLL/HA films was examined. Evaluation of photoreceptor cell viability was optimal on one layer of PLL (PLL(1)), followed by 10 bilayers of PLL/HA [(PLL/HA)(10)] and 10 bilayers of PLL/CSA [(PLL/CSA)(10)]. The number of bilayers and the type of terminating layer also had a significant influence on the number of photoreceptor cells attached. Functionalized polyelectrolyte multilayer films were obtained by adsorbing basic fibroblastic factor (bFGF) or the insoluble fraction of interphotoreceptor matrix (IPM) on or within polyelectrolyte multilayers. bFGF and IPM adsorption on top of the (PLL/CSA)(10)/PLL polyelectrolyte films increased the number of photoreceptor cells attached and maintained the differentiation of rod and cone cells.

Animals↗
PubMed2006

Polyelectrolyte nanoparticles with high drug loading enhance the oral uptake of hydrophobic compounds.

In the pharmaceutical industry, orally active compounds are required to have sufficient water solubility to enable dissolution within the gastrointestinal tract prior to absorption. Limited dissolution within the gastrointestinal tract often reduces the bioavailability of hydrophobic drugs. To improve gastrointestinal tract dissolution, nonaqueous solvents are often used in the form of emulsions and microemulsions. Here, we show that oil-free polyelectrolyte nanosystems (micellar dispersions and 100-300 nm particles) prepared from poly(ethylenimines) derivatized with cetyl chains and quaternary ammonium groups are able to encapsulate high levels of hydrophobic drug (0.20 g of drug per g of polymer) for over 9 months, as demonstrated using cyclosporine A (log P = 4.3). The polyelectrolytes facilitate the absorption of hydrophobic drugs within the gastrointestinal tract by promoting drug dissolution and by a hypothesized mechanism involving paracellular drug transport. Polyelectrolyte nanoparticle drug blood levels are similar to those obtained with commercial microemulsion formulations. The polyelectrolytes do not promote absorption by inhibition of the P-glycoprotein efflux pump.

Administration, Oral↗
PubMed2003

Ordered polyelectrolyte multilayers. Rules governing layering in organic binary multilayers.

We study the growth and internal structure of polyelectrolyte multilayers obtained by combining three polyanions with nine polycations of the ionene family, of systematically varied chemical architecture. We find that, contrary to a generally held belief, ordered organic multilayers are by no way exceptional, provided one of the polyelectrolytes bears groups which induce structure in water, such as long hydrophobic segments or mesogenic groups. However, this condition is not sufficient, as order will or will not emerge in the multilayer depending on the specific pairing of the polyelectrolytes. The results support the notion that layering in the multilayer results from some degree of prestructuring of a water-swollen layer adsorbed during each step of deposition. These findings pave the way to new possible uses of polyelectrolyte multilayers, for example, for applications requiring preferential alignment or strong confinement of specific functional groups.

Journal Article↗
PubMed2004

Luminescence quenching of a phosphorescent conjugated polyelectrolyte.

The photophysical and luminescence quenching properties of a platinum(II) acetylide-based conjugated polyelectrolyte, Pt-p, which features carboxylic acid solubilizing groups are reported. The Pt-acetylide polymer is water soluble, and it exhibits phosphorescence from a triplet pi,pi exciton based on the conjugated backbone. The phosphorescence from Pt-p is quenched by viologens with different charges (MV(+), MV(2+), and MV(4+)), and in each case the quenching is dominated by a dynamic (diffusional) mechanism. Comparison of the Stern-Volmer quenching properties of Pt-p with those of a structurally analogous fluorescent organic polyelectrolyte leads to the conclusion that the amplified quenching effect, which is commonly observed for fluorescent conjugated polyelectrolytes, is not important for the platinum acetylide phosphorescent conjugated polyelectrolyte.

Journal Article↗
PubMed2005

A modified Poisson-Boltzmann model including charge regulation for the adsorption of ionizable polyelectrolytes to charged interfaces, applied to lysozyme adsorption on silica.

The equilibrium adsorption of polyelectrolytes with multiple types of ionizable groups is described using a modified Poisson-Boltzmann equation including charge regulation of both the polymer and the interface. A one-dimensional mean-field model is used in which the electrostatic potential is assumed constant in the lateral direction parallel to the surface. The electrostatic potential and ionization degrees of the different ionizable groups are calculated as function of the distance from the surface after which the electric and chemical contributions to the free energy are obtained. The various interactions between small ions, surface and polyelectrolyte are self-consistently considered in the model, such as the increase in charge of polyelectrolyte and surface upon adsorption as well as the displacement of small ions and the decrease of permittivity. These interactions may lead to complex dependencies of the adsorbed amount of polyelectrolyte on pH, ionic strength, and properties of the polymer (volume, permittivity, number, and type of ionizable groups) and of the surface (number of ionizable groups, pK, Stern capacity). For the adsorption of lysozyme on silica, the model qualitatively describes the gradual increase of adsorbed amount with pH up to a maximum value at pHc, which is below the iso-electric point, as well as the sharp decrease of adsorbed amount beyond pHc. With increasing ionic strength the adsorbed amount decreases (for pH > pHc), and pHc shifts to lower values.

Adsorption↗
PubMed2006

Reversible association of thermoresponsive gold nanoparticles: polyelectrolyte effect on the lower critical solution temperature of poly(vinyl methyl ether).

Thermoresponsive gold nanoparticles (GNPs) have been prepared by the borohydride reduction of gold salt in the presence of water-soluble polymer, poly(vinyl methyl ether) (PVME). The PVME-coated GNPs (PVME-GNPs) have been assembled into large aggregates in the presence of polyelectrolytes, viz., poly(sodium-4 styrene sulfonate) and sodium salt of carboxymethylcellulose at low pH by raising the solution temperature from 20 to 40 degrees C. Increase of temperature triggers the interparticle association due to hydrophobic interaction of pendent methyl group of the surface adsorbed PVME. This assembly process is reversible with respect to temperature and pH of the medium and was studied by monitoring the change in surface plasmon resonance band of PVME-GNPs. Three-dimensional assemblies of various architectures, depending on the concentration of polyelectrolytes, were observed through transmission electron microscopy. A mechanistic model has been suggested for the reversible assembly formation that suits well with the experimental observations. The changes in optical properties of the PVME-GNPs due to their aggregation/disaggregation enabled us to use it as an effective tool to monitor the change in lower critical solution temperature (LCST) of PVME in the presence of polyelectrolytes due to interpolymer complexation at low pH. This result agrees well with the variation of LCST of pure aqueous PVME solution in the presence of polyelectrolytes measured by conventional turbidimetric technique.

Journal Article↗
PubMed2006

Density functional theory for planar electric double layers: closing the gap between simple and polyelectrolytes.

We report a nonlocal density functional theory (NLDFT) for polyelectrolyte solutions within the primitive model; i.e., the solvent is represented by a continuous dielectric medium, and the small ions and polyions by single and tangentially connected charged hard spheres, respectively. The excess Helmholtz energy functional is derived from a modified fundamental measure theory for hard-sphere repulsion, an extended first-order thermodynamic perturbation theory for chain connectivity, and a quadratic functional Taylor expansion for electrostatic correlations. With the direct and cavity correlation functions of the corresponding monomeric systems as inputs, the NLDFT predicts the segment-level microscopic structures and adsorption isotherms of polyelectrolytes at oppositely charged surfaces in good agreement with molecular simulations. In particular, it faithfully reproduces the layering structures of polyions, charge inversion, and overcharging that cannot be captured by alternative methods including the polyelectrolyte Poisson-Boltzmann equation and an earlier version of DFT. The NLDFT has also been used to investigate the influences of the small ion valence, polyion chain length, and size disparity between polyion segments and counterions on the microscopic structure, mean electrostatic potential, and overcharging in planar electric double layers containing polyelectrolytes.

Journal Article↗
PubMed2004

Permeability and conductivity of red blood cell templated polyelectrolyte capsules coated with supplementary layers.

The permeability of ions and small polar molecules through polyelectrolyte multilayer capsules templated on red blood cells was studied by means of confocal microscopy and electrorotation. Capsules were obtained by removing the cell after polyelectrolyte multilayer formation by means of NaOCl treatment. This procedure results in cross-linking of poly(allylamine hydrochloride) (PAH) molecules and destroying poly(styrene sulfonate) (PSS) within the multilayer. Capsules are obtained being remarkably different from layer-by-layer (LbL) capsules. These capsules are rather permeable for low as well as for high molecular weight species. However, upon adsorption of extra polyelectrolyte layers the permeability decreased remarkably. The assembly of six supplementary layers of PAH and PSS rendered the capsule almost impermeable for fluorescein. Resealing by supplementary layers is a potential means for filling and release control. By means of electrorotation measurements, it was shown that the capsule walls obtained isolating properties in electrolyte solutions. Conclusions are drawn concerning the mechanism of permeability through cell templated polyelectrolyte multilayer capsules.

Capsules↗
PubMed2005

Super-stoichiometric charge neutralization in particle-polyelectrolyte systems.

The adsorption of poly(vinylamine) (PVA) on poly(styrene sulfate) latex particles is studied, and its consequences on the charging behavior and suspension stability are investigated. The adsorption process is assessed by batch depletion experiments and time-resolved electrophoretic mobility measurements. The adsorption of PVA appears to be basically irreversible. The rate of adsorption decreases with decreasing polymer dose. At low polymer dose, the polymer coverage corresponds to the amount of the polyelectrolyte added, while at high polymer dose, the polymer coverage saturates the surface. Stability ratios are determined by dynamic light scattering, and strongly depend on the polymer dose and salt level. The aggregation is rapid near the isoelectric point (IEP), and it slows down when moving away from it. The charge neutralization is highly nonstoichiometric with charging ratios (CR) larger than unity, meaning that several charges on an adsorbed polyelectrolyte chain are necessary to neutralize a single charge on the particle surface. By comparing the IEP for particles and polyelectrolytes of different charge densities, we find a strong dependence of the CR on the mismatch between the average distances between individual charges on the surface and on the polyelectrolyte. A simple model is proposed to explain this trend.

Journal Article↗
PubMed2005

Phase behavior and rheological properties of polyelectrolyte inks for direct-write assembly.

Three-dimensional (3-D) structures with micron-sized features have been fabricated via the direct-write assembly of polyelectrolyte inks. By mixing oppositely charged species under solution conditions that promote polyelectrolyte exchange reactions, we have created concentrated fluids capable of flowing through microscale deposition nozzles. Ink deposition into an alcohol/water coagulation reservoir yielded polyelectrolyte filaments that rapidly solidify to enable three-dimensional patterning of microperiodic structures with self-supporting features. The influence of ink and reservoir chemistry on the phase behavior, rheological properties, and assembly of concentrated polyelectrolyte complexes is reported with an emphasis on the optimal conditions for 3-D writing.

Journal Article↗
PubMed2004

Mechanical properties of polyelectrolyte-filled multilayer microcapsules studied by atomic force and confocal microscopy.

By using a combination of atomic force and confocal microscopy, we explore the deformation properties of multilayer microcapsules filled with a solution of strong polyelectrolyte. Encapsulation of polyelectrolyte was performed by regulation of the multilayer shell permeability in water-acetone solutions. The "filled"capsules prepared by this method were found to be stiffer than "hollow" ones, which reflects the contribution of the excess osmotic pressure to the capsule stiffness. The force-deformation curves contain three distinct regimes of reversible, partially reversible, and irreversible deformations depending on the degree of compression. The analysis of the shape of compressed capsules and of the inner polyelectrolyte spacial distribution allowed one to relate the deformation regimes to the permeability of the multilayer shells for water and inner polyelectrolyte at different stage of compression.

Acetone↗
PubMed2004

Manipulation of the adsorption of ionic surfactants onto hydrophilic silica using polyelectrolytes.

This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.

Journal Article↗
PubMed2004

Surface interactions during polyelectrolyte multilayer buildup. 1. Interactions and layer structure in dilute electrolyte solutions.

We report the investigation of surface forces between polyelectrolyte multilayers of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) assembled on mica surfaces during film buildup using a surface force apparatus. Up to four polyelectrolyte layers were prepared on each surface ex situ, and the surface interactions were measured in 10(-4) M KBr solutions. The film thickness under high compressive loads (above 2000 microN/m) increased linearly with the number of deposited layers. In all cases, the interaction between identical surfaces at large separations (>100 A from contact) was dominated by electrostatic double-layer repulsion. By fitting DLVO theory to the experimental force curves, the apparent double-layer potential of the interacting surfaces was calculated. At shorter separations, an additional non-DLVO repulsion was present due to polyelectrolyte chains extending some distance from the surface into solution, thus generating an electrosteric type of repulsion. Forces between dissimilar multilayers (i.e., one of the multilayers terminated with PSS and the other with PAH) were attractive at large separations (30-400 A) owing to a combination of electrostatic attraction and polyelectrolyte bridging.

Journal Article↗
PubMed2005

Polyelectrolyte gel transitions: experimental aspects of charge inhomogeneity in the swelling and segmental attractions in the shrinking.

This paper aims to provide a systematic discussion based on our experimental results both previously published and unpublished, to promote better understanding of volume-phase transitions in polyelectrolyte gels. Special attention was paid to the distribution of network charges as well as to the attractive interaction among polymer segments. From looking at how these effects appear in the swelling curves, an exploration of the nature of polyelectrolyte gel transitions was attempted. Two sorts of polyelectrolyte gels, temperature-responsive ionic gels based on N-isopropylacrylamide (NIPA) and cationic poly(ethyleneimine) (PEI) gels, were mainly employed with various modifications. The charge inhomogeneity within the gel phase was created by surfactant binding, immobilized enzyme reaction and physical entrapment of polyions. The attractive interactions holding the gel in a collapsed state were studied in comparison with phase separations of the corresponding linear polyelectrolyte. The main conclusions are summarized as follows: (i) The charge inhomogeneity exhibits a large influence on the volume transition in ionic gels. (ii) Hydrogen bonding and hydrophobic association, other than electrostatic attraction, can be considered to play an important role in the segmental association. (iii) Stably associated segments via one or more of these attractive interactions causes a large hysteresis in the swelling process, in which the repulsive interaction among the fixed charges on the network is dominant as shown in the Katchalsky's model. (iv) A distribution of "neutral but hydrophilic" moieties (e.g., ion pair or salt-linkage formed between the opposite charged groups) within the gel shows a marked effect on the temperature-induced volume collapse, the aspect of which is similar to that observed in the gels with a charge inhomogeneity.

Acrylamides↗
PubMed2005

Mixed systems of hydrophobically modified polyelectrolytes: controlling rheology by charge and hydrophobe stoichiometry and interaction strength.

Rheology and phase separation were investigated for aqueous mixtures of two oppositely charged hydrophobically modified polyelectrolytes. The typical phase separation, normally seen for oppositely charged polymer mixtures, is dramatically reduced by the presence of hydrophobic modification, and phase separation is only detected close to the point of charge neutralization. While the two polyelectrolytes separately can give high viscosities and a gel-like behavior, a pronounced maximum in viscosity and storage modulus with the mixing ratio of the polyelectrolytes is observed; the maximum is located between the points of charge and hydrophobe stoichiometry and reflects a combination of hydrophobic and electrostatic association. Lowering the charge density of the anionic polymer leads to a strengthened association at first, but at lower charge densities there is a weakened association due to the onset of phase separation. The strength of the electrostatic interaction was modified by adding salt. Increased ionic strength can lead to phase separation and to increased or decreased viscosity depending on the polyelectrolyte mixing ratio.

Journal Article↗
PubMed2005

Polyelectrolyte-protein complexes: structure and conformation of each specie revealed by SANS.

We report here the structure of complexes made of proteins (lysozyme, positively charged) and polyelectrolytes (PSSNa, negatively charged). We stay in conditions where the volume fractions of the components are of the same order and where PSS concentrations correspond to a semidilute regime. The final complexes structure is determined by SANS. We obtain three main types of structures: (i) For a protein excess and for long polyelectrolyte chains, the network preformed by PSS chains still exists but chains are partially shrunk due to cross-linking by lysozyme. Macroscopically, samples are gelled. (ii) For a protein excess and for short polyelectrolyte chains, PSS chains are locally shrunk and do not form a network anymore. Lysozyme and PSS chains are embedded in dense 3-D aggregates that arrange in a fractal network at a larger scale. Macroscopically, samples are liquid. (iii) For a polyelectrolyte excess and whatever the chain length, the internal structure of the lysozyme changes. After an initial strong electrostatic binding, lysozyme is progressively unfolded thanks to a hydrophobic contact with PSS. The two chainlike objects are finally organized in a homogeneous costructure. Macroscopically, samples are liquids.

Electrolytes↗