Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

NASA Astrophysics Data System (ADS)

Plucktaveesak, Nopparat

The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly(styrene-alt-sodium maleate) and poly(diisobutylene- alt-sodium maleate) show the polyelectrolyte behavior as predicted. However, the viscosity as a function of concentration of sodium maleate based copolymers with 1-alkenes; 1-octene (C8), 1-decene (C10), 1-dodecene (C12) and 1-hexene (C14) exhibit an abnormal scaling power, which might be caused by aggregation of the alkene tails to form micelles. In the last chapter, we report the rheological properties of aqueous solutions of poly(acrylic acid) and oppositely charged surfactant, dodecyl trimethylammonium bromide (C12TAB). The solution viscosity decreases as surfactant is added, partly because the polyelectrolyte wraps around the surface of the spherical surfactant micelles, shortening the effective chain length. The effects of polymer molecular weight, polymer concentration, and polymer charge have been studied with no added salt. The results are compared with the predictions of a simple model based on the scaling theory for the viscosity of dilute and unentangled semidilute polyelectrolyte solutions in good solvent. This model takes into account two effects of added surfactant. The effective chain length of the polyelectrolyte is shortened when a significant fraction of the chain wraps around micelles. Another effect is the change of solution ionic strength resulting from surfactant addition that further lowers the viscosity. The parameters used in this model are independently determined, allowing the model to make a quantitative prediction of solution viscosity with no adjustable parameters. The model is also applied to predict the decrease in viscosity of various polyelectrolyte/oppositely charged surfactant systems reported in literature. The results are in good agreement with experimental data, proving that our model applies to all polyelectrolytes mixed with oppositely charged surfactants that form spherical micelles.

50th Anniversary Perspective: A Perspective on Polyelectrolyte Solutions

PubMed Central

2017-01-01

From the beginning of life with the information-containing polymers until the present era of a plethora of water-based materials in health care industry and biotechnology, polyelectrolytes are ubiquitous with a broad range of structural and functional properties. The main attribute of polyelectrolyte solutions is that all molecules are strongly correlated both topologically and electrostatically in their neutralizing background of charged ions in highly polarizable solvent. These strong correlations and the necessary use of numerous variables in experiments on polyelectrolytes have presented immense challenges toward fundamental understanding of the various behaviors of charged polymeric systems. This Perspective presents the author’s subjective summary of several conceptual advances and the remaining persistent challenges in the contexts of charge and size of polymers, structures in homogeneous solutions, thermodynamic instability and phase transitions, structural evolution with oppositely charged polymers, dynamics in polyelectrolyte solutions, kinetics of phase separation, mobility of charged macromolecules between compartments, and implications to biological systems. PMID:29296029

Influence of Protamine Functionalization on the Colloidal Stability of 1D and 2D Titanium Oxide Nanostructures.

PubMed

Rouster, Paul; Pavlovic, Marko; Horváth, Endre; Forró, László; Dey, Sandwip K; Szilagyi, Istvan

2017-09-26

The colloidal stability of titanium oxide nanosheets (TNS) and nanowires (TiONW) was studied in the presence of protamine (natural polyelectrolyte) in aqueous dispersions, where the nanostructures possessed negative net charge, and the protamine was positively charged. Regardless of their shape, similar charging and aggregation behaviors were observed for both TNS and TiONW. Electrophoretic experiments performed at different protamine loadings revealed that the adsorption of protamine led to charge neutralization and charge inversion depending on the polyelectrolyte dose applied. Light scattering measurements indicated unstable dispersions once the surface charge was close to zero or slow aggregation below and above the charge neutralization point with negatively or positively charged nanostructures, respectively. These stability regimes were confirmed by the electron microscopy images taken at different polyelectrolyte loadings. The protamine dose and salt-dependent colloidal stability confirmed the presence of DLVO-type interparticle forces, and no experimental evidence was found for additional interactions (e.g., patch-charge, hydrophobic, or steric forces), which are usually present in similar polyelectrolyte-particle systems. These findings indicate that the polyelectrolyte adsorbs on the TNS and TiONW surfaces in a flat and extended conformation giving rise to the absence of surface heterogeneities. Therefore, protamine is an excellent biocompatible candidate to form smooth surfaces, for instance in multilayers composed of polyelectrolytes and particles to be used in biomedical applications.

Adsorption of surfactants and polymers at interfaces

NASA Astrophysics Data System (ADS)

Rojas, Orlando Jose

Surface tension and high-resolution laser light scattering experiments were used to investigate the adsorption of isomeric sugar-based surfactants at the air/liquid interface in terms of surfactant surface packing and rheology. Soluble monolayers of submicellar surfactant solutions exhibited a relatively viscous behavior. It was also proved that light scattering of high-frequency thermally-induced capillary waves can be utilized to study surfactant exchange between the surface and the bulk solution. Such analysis revealed the existence of a diffusional relaxation mechanism. A procedure based on XPS was developed for quantification, on an absolute basis, of polymer adsorption on mica and Langmuir-Blodgett cellulose films. The adsorption of cationic polyelectrolytes on negatively-charged solid surfaces was highly dependent on the polymer ionicity. It was found that the adsorption process is driven by electrostatic mechanisms. Charge overcompensation (or charge reversal) of mica occurred after adsorption of polyelectrolytes of ca. 50% charge density, or higher. It was demonstrated that low-charge-density polyelectrolytes adsorb on solid surfaces with an extended configuration dominated by loops and tails. In this case the extent of adsorption is limited by steric constraints. The conformation of the polyelectrolyte in the adsorbed layer is dramatically affected by the presence of salts or surfactants in aqueous solution. The phenomena which occur upon increasing the ionic strength are consistent with the screening of the electrostatic attraction between polyelectrolyte segments and solid surface. This situation leads to polyelectrolyte desorption accompanied by both an increase in the layer thickness and the range of the steric force. Adsorbed polyelectrolytes and oppositely charged surfactants readily associate at the solid/liquid interface. Such association induces polyelectrolyte desorption at a surfactant concentration which depends on the polyelectrolyte charge density. In practical systems the adsorption phenomena were found to be far more complex. Electrostatic and hydrogen bonding interactions play a major role in the adsorption of cationic polyelectrolytes on cellulosic substrates. Cationic and underivatized guar gum macromolecules form complexes with fines and dissolved and colloidal carbohydrates which are then retained on the cellulose fibers. The extent of the adsorption and association depends on the charge and nature of all the components present in pulp suspensions.

Polyelectrolytes and Their Biological Interactions

PubMed Central

Katchalsky, A.

1964-01-01

Polyelectrolytes are water-soluble electrically charged polymers. Their properties are determined by the interplay of the electrical forces, the Brownian motion of the macromolecular chain, and intermolecular Van der Waals forces. Charged polyacids or polybases are stretched by the electrostatic forces, as evidenced by increase in solution viscosity, or by the stretching of polyelectrolyte gels. The electrical field of the polyions is neutralized by a dense atmosphere of counter-ions. The counter-ion attraction to the polyions is expressed by a reduction of the osmotic activity of the polyion—the osmotic pressure being only 15 to 20 per cent of the ideal in highly charged polyelectrolytes neutralized by monovalent counter-ions, and as low as 1 to 3 per cent of the ideal for polyvalent counter-ions. Since the ionic atmosphere is only slightly dependent on added low molecular salt, the osmotic pressure of polyelectrolyte salt mixtures is approximately equal to the sum of the osmotic pressure of polyelectrolyte and salt alone. Acidic and basic polyelectrolytes interact electrostatically with precipitation at the point of polymeric electroneutrality. At higher salt concentrations the interaction is inhibited by the screening of polymeric fixed charges. The importance of these interactions in enzymatic processes is discussed. The electrical double layer is polarizable as may be deduced from dielectric and conductometric studies. The polarizability leads to strong dipole formation in an electrical field. These macromolecular dipoles may play a role in the adsorption of polyelectrolytes on charged surfaces. The final part of the paper is devoted to interactions of polyelectrolytes with cell membranes and the gluing of cells to higher aggregates by charged biocolloids. ImagesFigure 17Figure 18Figure 19Figure 20 PMID:14104085

Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

PubMed Central

Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

2009-01-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

Mechanisms of polyelectrolyte enhanced surfactant adsorption at the air-water interface.

PubMed

Stenger, Patrick C; Palazoglu, Omer A; Zasadzinski, Joseph A

2009-05-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids.

Advances in polyelectrolyte multilayer nanofilms as tunable drug delivery systems

PubMed Central

Jiang, Bingbing; Barnett, John B; Li, Bingyun

2009-01-01

There has been considerable interest in polyelectrolyte multilayer nanofilms, which have a variety of applications ranging from optical and electrochemical materials to biomedical devices. Polyelectrolyte multilayer nanofilms are constructed from aqueous solutions using electrostatic layer-by-layer self-assembly of oppositely-charged polyelectrolytes on a solid substrate. Multifunctional polyelectrolyte multilayer nanofilms have been studied using charged dyes, metal and inorganic nanoparticles, DNA, proteins, and viruses. In the past few years, there has been increasing attention to developing polyelectrolyte multilayer nanofilms as drug delivery vehicles. In this mini-review, we present recent developments in polyelectrolyte multilayer nanofilms with tunable drug delivery properties, with particular emphasis on the strategies in tuning the loading and release of drugs in polyelectrolyte multilayer nanofilms as well as their applications. PMID:24198464

Effect of PEG-PDMAEMA Block Copolymer Architecture on Polyelectrolyte Complex Formation with Heparin.

PubMed

Välimäki, Salla; Khakalo, Alexey; Ora, Ari; Johansson, Leena-Sisko; Rojas, Orlando J; Kostiainen, Mauri A

2016-09-12

Heparin is a naturally occurring polyelectrolyte consisting of a sulfated polysaccharide backbone. It is widely used as an anticoagulant during major surgical operations. However, the associated bleeding risks require rapid neutralization after the operation. The only clinically approved antidote for heparin is protamine sulfate, which is, however, ineffective against low molecular weight heparin and can cause severe adverse reactions in patients. In this study, the facile synthesis of cationic-neutral diblock copolymers and their effective heparin binding is presented. Poly(ethylene glycol)-poly(2-(dimethylamino)ethyl methacrylate) (PEG-PDMAEMA) block copolymers were synthesized in two steps via atom-transfer radical polymerization (ATRP) using PEG as a macroinitiator. Solution state binding between heparin and a range of PEG-PDMAEMA block copolymers and one homopolymer was studied with dynamic light scattering and methylene blue displacement assay. Also in vitro binding in plasma was studied by utilizing a chromogenic heparin anti-Xa assay. Additionally, quartz crystal microbalance and multiparametric surface plasmon resonance were used to study the surface adsorption kinetics of the polymers on a heparin layer. It was shown that the block copolymers and heparin form electrostatically bound complexes with varying colloidal properties, where the block lengths play a key role in controlling the heparin binding affinity, polyelectrolyte complex size and surface charge. With the optimized polymers (PEG114PDMAEMA52 and PEG114PDMAEMA100), heparin could be neutralized in a dose-dependent manner, and bound efficiently into small neutral complexes, with a hydrodynamic radius less than 100 nm. These complexes had only a limited effect on cell viability. Based on these studies, our approach paves the way for the development of new polymeric heparin binding agents.

Motion-based, high-yielding, and fast separation of different charged organics in water.

PubMed

Xuan, Mingjun; Lin, Xiankun; Shao, Jingxin; Dai, Luru; He, Qiang

2015-01-12

We report a self-propelled Janus silica micromotor as a motion-based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self-propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s(-1) . Biotin-functionalized Janus micromotors can specifically capture and rapidly transport streptavidin-modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self-propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab-on-chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poisson-Boltzmann theory of the charge-induced adsorption of semi-flexible polyelectrolytes.

PubMed

Ubbink, Job; Khokhlov, Alexei R

2004-03-15

A model is suggested for the structure of an adsorbed layer of a highly charged semi-flexible polyelectrolyte on a weakly charged surface of opposite charge sign. The adsorbed phase is thin, owing to the effective reversal of the charge sign of the surface upon adsorption, and ordered, owing to the high surface density of polyelectrolyte strands caused by the generally strong binding between polyelectrolyte and surface. The Poisson-Boltzmann equation for the electrostatic interaction between the array of adsorbed polyelectrolytes and the charged surface is solved for a cylindrical geometry, both numerically, using a finite element method, and analytically within the weak curvature limit under the assumption of excess monovalent salt. For small separations, repulsive surface polarization and counterion osmotic pressure effects dominate over the electrostatic attraction and the resulting electrostatic interaction curve shows a minimum at nonzero separations on the Angstrom scale. The equilibrium density of the adsorbed phase is obtained by minimizing the total free energy under the condition of equality of chemical potential and osmotic pressure of the polyelectrolyte in solution and in the adsorbed phase. For a wide range of ionic conditions and charge densities of the charged surface, the interstrand separation as predicted by the Poisson-Boltzmann model and the analytical theory closely agree. For low to moderate charge densities of the adsorbing surface, the interstrand spacing decreases as a function of the charge density of the charged surface. Above about 0.1 M excess monovalent salt, it is only weakly dependent on the ionic strength. At high charge densities of the adsorbing surface, the interstrand spacing increases with increasing ionic strength, in line with the experiments by Fang and Yang [J. Phys. Chem. B 101, 441 (1997)]. (c) 2004 American Institute of Physics.

Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers.

PubMed

Nap, R J; Tagliazucchi, M; Szleifer, I

2014-01-14

This work addresses the effect of the Born self-energy contribution in the modeling of the structural and thermodynamical properties of weak polyelectrolytes confined to planar and curved surfaces. The theoretical framework is based on a theory that explicitly includes the conformations, size, shape, and charge distribution of all molecular species and considers the acid-base equilibrium of the weak polyelectrolyte. Namely, the degree of charge in the polymers is not imposed but it is a local varying property that results from the minimization of the total free energy. Inclusion of the dielectric properties of the polyelectrolyte is important as the environment of a polymer layer is very different from that in the adjacent aqueous solution. The main effect of the Born energy contribution on the molecular organization of an end-grafted weak polyacid layer is uncharging the weak acid (or basic) groups and consequently decreasing the concentration of mobile ions within the layer. The magnitude of the effect increases with polymer density and, in the case of the average degree of charge, it is qualitatively equivalent to a small shift in the equilibrium constant for the acid-base equilibrium of the weak polyelectrolyte monomers. The degree of charge is established by the competition between electrostatic interactions, the polymer conformational entropy, the excluded volume interactions, the translational entropy of the counterions and the acid-base chemical equilibrium. Consideration of the Born energy introduces an additional energetic penalty to the presence of charged groups in the polyelectrolyte layer, whose effect is mitigated by down-regulating the amount of charge, i.e., by shifting the local-acid base equilibrium towards its uncharged state. Shifting of the local acid-base equilibrium and its effect on the properties of the polyelectrolyte layer, without considering the Born energy, have been theoretically predicted previously. Account of the Born energy leads to systematic, but in general small, corrections to earlier theoretical predictions describing the behavior of weak polyelectrolyte layers. However, polyelectrolyte uncharging results in a decrease in the concentration of counterions and inclusion of the Born Energy can result in a substantial decrease of the counterion concentration. The effect of considering the Born energy contribution is explored for end-grafted weak polyelectrolyte layers by calculating experimental observables which are known to depend on the presence of charges within the polyelectrolyte layer: inclusion of the Born energy contribution leads to a decrease in the capacitance of polyelectrolyte-modified electrodes, a decrease of conductivity of polyelectrolyte-modified nanopores and an increase in the repulsion exerted by a planar polyelectrolyte layer confined by an opposing wall.

Complex coacervation of supercharged proteins with polyelectrolytes.

PubMed

Obermeyer, Allie C; Mills, Carolyn E; Dong, Xue-Hui; Flores, Romeo J; Olsen, Bradley D

2016-04-21

Complexation of proteins with polyelectrolytes or block copolymers can lead to phase separation to generate a coacervate phase or self-assembly of coacervate core micelles. However, many proteins do not coacervate at conditions near neutral pH and physiological ionic strength. Here, protein supercharging is used to systematically explore the effect of protein charge on the complex coacervation with polycations. Four model proteins were anionically supercharged to varying degrees as quantified by mass spectrometry. Proteins phase separated with strong polycations when the ratio of negatively charged residues to positively charged residues on the protein (α) was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger α (1.5-2.0). The preferred charge ratio for coacervation was shifted away from charge symmetry for three of the four model proteins and indicated an excess of positive charge in the coacervate phase. The composition of protein and polymer in the coacervate phase was determined using fluorescently labeled components, revealing that several of the coacervates likely have both induced charging and a macromolecular charge imbalance. The model proteins were also encapsulated in complex coacervate core micelles and micelles formed when the protein charge ratio α was greater than 1.3-1.4. Small angle neutron scattering and transmission electron microscopy showed that the micelles were spherical. The stability of the coacervate phase in both the bulk and micelles improved to increased ionic strength as the net charge on the protein increased. The micelles were also stable to dehydration and elevated temperatures.

Biosensors from conjugated polyelectrolyte complexes

PubMed Central

Wang, Deli; Gong, Xiong; Heeger, Peter S.; Rininsland, Frauke; Bazan, Guillermo C.; Heeger, Alan J.

2002-01-01

A charge neutral complex (CNC) was formed in aqueous solution by combining an orange light emitting anionic conjugated polyelectrolyte and a saturated cationic polyelectrolyte at a 1:1 ratio (per repeat unit). Photoluminescence (PL) from the CNC can be quenched by both the negatively charged dinitrophenol (DNP) derivative, (DNP-BS−), and positively charged methyl viologen (MV2+). Use of the CNC minimizes nonspecific interactions (which modify the PL) between conjugated polyelectrolytes and biopolymers. Quenching of the PL from the CNC by the DNP derivative and specific unquenching on addition of anti-DNP antibody (anti-DNP IgG) were observed. Thus, biosensing of the anti-DNP IgG was demonstrated. PMID:11756675

Complexation of lysozyme with adsorbed PtBS-b-SCPI block polyelectrolyte micelles on silver surface.

PubMed

Papagiannopoulos, Aristeidis; Christoulaki, Anastasia; Spiliopoulos, Nikolaos; Vradis, Alexandros; Toprakcioglu, Chris; Pispas, Stergios

2015-01-20

We present a study of the interaction of the positively charged model protein lysozyme with the negatively charged amphiphilic diblock polyelectrolyte micelles of poly(tert-butylstyrene-b-sodium (sulfamate/carboxylate)isoprene) (PtBS-b-SCPI) on the silver/water interface. The adsorption kinetics are monitored by surface plasmon resonance, and the surface morphology is probed by atomic force microscopy. The micellar adsorption is described by stretched-exponential kinetics, and the micellar layer morphology shows that the micelles do not lose their integrity upon adsorption. The complexation of lysozyme with the adsorbed micellar layers depends on the micelles arrangement and density in the underlying layer, and lysozyme follows the local morphology of the underlying roughness. When the micellar adsorbed amount is small, the layers show low capacity in protein complexation and low resistance in loading. When the micellar adsorbed amount is high, the situation is reversed. The adsorbed layers both with or without added protein are found to be irreversibly adsorbed on the Ag surface.

Electrostatic Interactions and Self-Assembly in Polymeric Systems

NASA Astrophysics Data System (ADS)

Dobrynin, Andrey

Electrostatic interactions between macroions play an important role in different areas ranging from materials science to biophysics. They are main driving forces behind layer-by-layer assembly technique that allows self-assembly of multilayer films from synthetic polyelectrolytes, DNA, proteins and nanoparticles. They are responsible for complexation and reversible gelation between polyelectrolytes and proteins. In this talk, using results of the molecular dynamics simulations and analytical calculations, I will demonstrate what effect electrostatic interactions, counterion condensation and polymer solvent affinity have on a collapse of polyelectrolyte chain in a poor solvent conditions for the polymer backbone, on complexations and reversible gelation between polyelectrolytes and polyamholytes (unstructured proteins), on microphase separation transitions in spherical and planar charged brushes, and on a layer-by-layer assembly of charged nanoparticles and linear polyelectrolytes on charged surfaces. NSF DMR-1004576 DMR-1409710.

Transient charge-masking effect of applied voltage on electrospinning of pure chitosan nanofibers from aqueous solutions.

PubMed

Terada, Dohiko; Kobayashi, Hisatoshi; Zhang, Kun; Tiwari, Ashutosh; Yoshikawa, Chiaki; Hanagata, Nobutaka

2012-02-01

The processing of a polyelectrolyte (whose functionality is derived from its ionized functional groups) into a nanofiber may improve its functionality and yield multiple functionalities. However, the electrospinning of nanofibers from polyelectrolytes is imperfect because polyelectrolytes differ considerably from neutral polymers in their rheological properties. In our study, we attempt to solve this problem by applying a voltage of opposite polarity to charges on a polyelectrolyte. The application of this 'countervoltage' can temporarily mask or screen a specific rheological property of the polyelectrolyte, making it behave as a neutral polymer. This approach can significantly contribute to the development of new functional nanofiber materials.

Synthetic polycations with controlled charge density and molecular weight as building blocks for biomaterials.

PubMed

Kleinberger, Rachelle M; Burke, Nicholas A D; Zhou, Christal; Stöver, Harald D H

2016-01-01

A series of polycations prepared by RAFT copolymerization of N-(3-aminopropyl)methacrylamide hydrochloride (APM) and N-(2-hydroxypropyl)methacrylamide, with molecular weights of 15 and 40 kDa, and APM content of 10-75 mol%, were tested as building blocks for electrostatically assembled hydrogels such as those used for cell encapsulation. Complexation and distribution of these copolymers within anionic calcium alginate gels, as well as cytotoxicity, cell attachment, and cell proliferation on surfaces grafted with the copolymers were found to depend on composition and molecular weight. Copolymers with lower cationic charge density and lower molecular weight showed less cytotoxicity and cell adhesion, and were more mobile within alginate gels. These findings aid in designing improved polyelectrolyte complexes for use as biomaterials.

Surface analysis monitoring of polyelectrolyte deposition on Ba 0.5Sr 0.5TiO 3 thin films

NASA Astrophysics Data System (ADS)

Morales-Cruz, Angel L.; Fachini, Estevão R.; Miranda, Félix A.; Cabrera, Carlos R.

2007-09-01

Thin films are currently gaining interest in many areas such as integrated optics, sensors, friction, reducing coatings, surface orientation layers, and general industrial applications. Recently, molecular self-assembling techniques have been applied for thin film deposition of electrically conducting polymers, conjugated polymers for light-emitting devices, nanoparticles, and noncentrosymmetric-ordered second order nonlinear optical (NOL) devices. Polyelectrolytes self-assemblies have been used to prepare thin films. The alternate immersion of a charged surface in polyannion and a polycation solution leads usually to the formation of films known as polyelectrolyte multilayers. These polyanion and polycation structures are not neutral. However, charge compensation appears on the surface. This constitutes the building driving force of the polyelectrolyte multilayer films. The present approach consists of two parts: (a) the chemisorption of 11-mercaptoundecylamine (MUA) to construct a self-assembled monolayer with the consequent protonation of the amine, and (b) the deposition of opposite charged polyelectrolytes in a sandwich fashion. The approach has the advantage that ionic attraction between opposite charges is the driving force for the multilayer buildup. For our purposes, the multilayer of polyelectrolytes depends on the quality of the surface needed for the application. In many cases, this approach will be used in a way that the roughness factor defects will be diminished. The polyelectrolytes selected for the study were: polystyrene sulfonate sodium salt (PSS), poly vinylsulfate potassium salt (PVS), and polyallylamine hydrochloride (PAH), as shown in Fig. 1. The deposition of polyelectrolytes was carried out by a dipping procedure with the corresponding polyelectrolyte. Monitoring of the alternate deposition of polyelectrolyte bilayers was done by surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), specular reflectance infrared (IR), and atomic force microscopy (AFM). The surface analysis results are presented through the adsorption steps of the polyelectrolytes layer by layer.

Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films

PubMed Central

Ball, Vincent

2012-01-01

Polyelectrolyte multilayer films are a versatile functionalization method of surfaces and rely on the alternated adsorption of oppositely charged species. Among such species, charged dyes can also be alternated with oppositely charged polymers, which is challenging from a fundamental point of view, because polyelectrolytes require a minimal number of charges, whereas even monovalent dyes can be incorporated during the alternated adsorption process. We will not only focus on organic dyes but also on their inorganic counterparts and on metal complexes. Such films offer plenty of possible applications in dye sensitized solar cells. In addition, dyes are massively used in the textile industry and in histology to stain textile fibers or tissues. However, the excess of non bound dyes poses serious environmental problems. It is hence of the highest interest to design materials able to adsorb such dyes in an almost irreversible manner. Polyelectrolyte multilayer films, owing to their ion exchange behavior can be useful for such a task allowing for impressive overconcentration of dyes with respect to the dye in solution. The actual state of knowledge of the interactions between charged dyes and adsorbed polyelectrolytes is the focus of this review article.

Simulations of free-solution electrophoresis of polyelectrolytes with a finite Debye length using the Debye-Hückel approximation.

PubMed

Hickey, Owen A; Shendruk, Tyler N; Harden, James L; Slater, Gary W

2012-08-31

We introduce a mesoscale simulation method based on multiparticle collision dynamics (MPCD) for the electrohydrodynamics of polyelectrolytes with finite Debye lengths. By applying the Debye-Hückel approximation to assign an effective charge to MPCD particles near charged monomers, our simulations are able to reproduce the rapid rise in the electrophoretic mobility with respect to the degree of polymerization for the shortest polymer lengths followed by a small decrease for longer polymers due to charge condensation. Moreover, these simulations demonstrate the importance of a finite Debye length in accurately determining the mobility of uniformly charged polyelectrolytes and net neutral polyampholytes.

Interaction between like-charged polyelectrolyte-colloid complexes in electrolyte solutions: a Monte Carlo simulation study in the Debye-Hückel approximation.

PubMed

Truzzolillo, D; Bordi, F; Sciortino, F; Sennato, S

2010-07-14

We study the effective interaction between differently charged polyelectrolyte-colloid complexes in electrolyte solutions via Monte Carlo simulations. These complexes are formed when short and flexible polyelectrolyte chains adsorb onto oppositely charged colloidal spheres, dispersed in an electrolyte solution. In our simulations the bending energy between adjacent monomers is small compared to the electrostatic energy, and the chains, once adsorbed, do not exchange with the solution, although they rearrange on the particles surface to accommodate further adsorbing chains or due to the electrostatic interaction with neighbor complexes. Rather unexpectedly, when two interacting particles approach each other, the rearrangement of the surface charge distribution invariably produces antiparallel dipolar doublets that invert their orientation at the isoelectric point. These findings clearly rule out a contribution of dipole-dipole interactions to the observed attractive interaction between the complexes, pointing out that such suspensions cannot be considered dipolar fluids. On varying the ionic strength of the electrolyte, we find that a screening length kappa(-1), short compared with the size of the colloidal particles, is required in order to observe the attraction between like-charged complexes due to the nonuniform distribution of the electric charge on their surface ("patch attraction"). On the other hand, by changing the polyelectrolyte/particle charge ratio xi(s), the interaction between like-charged polyelectrolyte-decorated particles, at short separations, evolves from purely repulsive to strongly attractive. Hence, the effective interaction between the complexes is characterized by a potential barrier, whose height depends on the net charge and on the nonuniformity of their surface charge distribution.

Structure of Weakly Charged Polyelectrolyte Brushes: Monomer Density Profiles

NASA Astrophysics Data System (ADS)

Borisov, O. V.; Zhulina, E. B.

1997-03-01

The internal structure (the monomer density profiles) of weakly charged polyelectrolyte brushes of different morphologies has been analyzed on the basis of the self-consistent-field approach. In contrast to previous studies based on the local electroneutrality approximation valid for sufficiently strongly charged or densely grafted (“osmotic") brushes we consider the opposite limit of sparse brushes which are unable to retain the counterions inside the brush. We have shown that an exact analytical solution of the SCF-equations is available in the case of a planar brush. In contrast to Gaussian monomer density profile known for “osmotic" polyelectrolyte brushes we have found that weakly charged brushes are characterized by constant monomer density. At the same time free ends of grafted polyions are distributed throughout the brush. Thus, the structural cross-over between polyelectrolyte “mushrooms" and dense brush regimes is established.

Regulation of anionic lipids in binary membrane upon the adsorption of polyelectrolyte: A Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Duan, Xiaozheng; Li, Yunqi; Zhang, Ran; Shi, Tongfei; An, Lijia; Huang, Qingrong

2013-06-01

We employ Monte Carlo simulations to investigate the interaction between an adsorbing linear flexible cationic polyelectrolyte and a binary fluid membrane. The membrane contains neutral phosphatidyl-choline, PC) and multivalent anionic (phosphatidylinositol, PIP2) lipids. We systematically study the influences of the solution ionic strength, the chain length and the bead charge density of the polyelectrolyte on the lateral rearrangement and the restricted mobility of the multivalent anionic lipids in the membrane. Our findings show that, the cooperativity effect and the electrostatic interaction of the polyelectrolyte beads can significantly affect the segregation extent and the concentration gradients of the PIP2 molecules, and further cooperate to induce the complicated hierarchical mobility behaviors of PIP2 molecules. In addition, when the polyelectrolyte brings a large amount of charges, it can form a robust electrostatic well to trap all PIP2 and results in local overcharge of the membrane. This work presents a mechanism to explain the membrane heterogeneity formation induced by the adsorption of charged macromolecule.

Self-assembled virus-membrane complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Lihua; Liang, Hongjun; Angelini, Thomas

Anionic polyelectrolytes and cationic lipid membranes can self-assemble into lamellar structures ranging from alternating layers of membranes and polyelectrolytes to 'missing layer' superlattice structures. We show that these structural differences can be understood in terms of the surface-charge-density mismatch between the polyelectrolyte and membrane components by examining complexes between cationic membranes and highly charged M13 viruses, a system that allowed us to vary the polyelectrolyte diameter independently of the charge density. Such virus-membrane complexes have pore sizes that are about ten times larger in area than DNA-membrane complexes, and can be used to package and organize large functional molecules; correlatedmore » arrays of Ru(bpy){sub 3}{sup 2+} macroionic dyes have been directly observed within the virus-membrane complexes using an electron-density reconstruction. These observations elucidate fundamental design rules for rational control of self-assembled polyelectrolyte-membrane structures, which have applications ranging from non-viral gene therapy to biomolecular templates for nanofabrication.« less

Charge Density Quantification of Polyelectrolyte Polysaccharides by Conductometric Titration: An Analytical Chemistry Experiment

ERIC Educational Resources Information Center

Farris, Stefano; Mora, Luigi; Capretti, Giorgio; Piergiovanni, Luciano

2012-01-01

An easy analytical method for determination of the charge density of polyelectrolytes, including polysaccharides and other biopolymers, is presented. The basic principles of conductometric titration, which is used in the pulp and paper industry as well as in colloid and interface science, were adapted to quantify the charge densities of a…

Elastin-like Polypeptide (ELP) Charge Influences Self-Assembly of ELP-mCherry Fusion Proteins.

PubMed

Mills, Carolyn E; Michaud, Zachary; Olsen, Bradley D

2018-05-23

Self-assembly of protein-polymer bioconjugates presents an elegant strategy for controlling nanostructure and orientation of globular proteins in functional materials. Recent work has shown that genetic fusion of globular protein mCherry to an elastin-like polypeptide (ELP) yields similar self-assembly behavior to these protein-polymer bioconjugates. In the context of studying protein-polymer bioconjugate self-assembly, the mutability of the ELP sequence allows several different properties of the ELP block to be tuned orthogonally while maintaining consistent polypeptide backbone chemistry. This work uses this ELP sequence tunability in combination with the precise control offered by genetic engineering of an amino acid sequence to generate a library of four novel ELP sequences that are used to study the combined effect of charge and hydrophobicity on ELP-mCherry fusion protein self-assembly. Concentrated solution self-assembly is studied by small-angle X-ray scattering (SAXS) and depolarized light scattering (DPLS). These experiments show that fusions containing a negatively charged ELP block do not assemble at all, and fusions with a charge balanced ELP block exhibit a weak propensity for assembly. By comparison, the fusion containing an uncharged ELP block starts to order at 40 wt % in solution and at all concentrations measured has sharper, more intense SAXS peaks than other fusion proteins. These experiments show that charge character of the ELP block is a stronger predictor of self-assembly behavior than the hydrophobicity of the ELP block. Dilute solution small-angle neutron scattering (SANS) on the ELPs alone suggests that all ELPs used in this study (including the uncharged ELP) adopt dilute solution conformations similar to those of traditional polymers, including polyampholytes and polyelectrolytes. Finally, dynamic light scattering studies on ELP-mCherry blends shows that there is no significant complexation between the charged ELPs and mCherry. Therefore, it is proposed that the superior self-assembly of fusion proteins containing uncharged ELP block is due to effective repulsions between charged and uncharged blocks due to local charge correlation effects and, in the case of anionic ELPs, repulsion between like charges within the ELP block.

Polyelectrolyte multilayers: preparation and applications

NASA Astrophysics Data System (ADS)

Izumrudov, V. A.; Mussabayeva, B. Kh; Murzagulova, K. B.

2018-02-01

The review concerns the results of studies on the synthesis of polyelectrolyte coatings on charged surfaces. These coatings represent nanostructured systems with clearly defined tendency to self-assembly and self-adjustment, which is of particular interest for materials science, biomedicine and pharmacology. A breakthrough in this area of knowledge is due to the development and introduction of a new technique, so-called layer-by-layer (LbL) deposition of nanofilms. The technique is very simple, viz., multilayers are formed as a result of alternating treatment of a charged substrate of arbitrary shape with water-salt solutions of differently charged polyelectrolytes. Nevertheless, efficient use of the LbL method to fabricate nanofilms requires meeting certain conditions and limitations that were revealed in the course of research on model systems. Prospects for applications of polyelectrolyte layers in various fields are discussed. The bibliography includes 58 references.

Reversible Adhesion with Polyelectrolyte Brushes Tailored via the Uptake and Release of Trivalent Lanthanum Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farina, Robert; Laugel, Nicolas; Yu, Jing

Applications of end-tethered polyelectrolyte “brushes” to modify solid surfaces have been developed and studied for their colloidal stabilization and high lubrication properties. Current efforts have expanded into biological realms and stimuli-responsive materials. Our work explores responsive and reversible aspects of polyelectrolyte brush behavior when polyelectrolyte chains interact with oppositely charged multivalent ions and complexes, which act as counterions. There is a significant void in the polyelectrolyte literature regarding interactions with multivalent species. This paper demonstrates that interactions between solid surfaces bearing negatively charged polyelectrolyte brushes are highly sensitive to the presence of trivalent lanthanum, La3+. Lanthanum cations have unique interactionsmore » with polyelectrolyte chains, in part due to their small size and hydration radius which results in a high local charge density. Using La3+ in conjunction with the surface forces apparatus (SFA), adhesion has been observed to reversibly appear and disappear upon the uptake and release, respectively, of these multivalent cations acting as counterions. In media of fixed ionic strength set by monovalent sodium salt, at I0 = 0.003 M and I0 = 0.3 M, the sign of the interaction forces between overlapping brushes changes from repulsive to attractive when La3+ concentrations reach 0.1 mol % of the total ion concentration. These results are also shown to be generally consistent with, but subtlety different from, previous polyelectrolyte brush experiments using trivalent ruthenium hexamine in the role of the multivalent counterion.« less

A study of properties of "micelle-enhanced" polyelectrolyte capsules: Structure, encapsulation and in vitro release.

PubMed

Li, Xiaodong; Lu, Tian; Zhang, Jianxiang; Xu, Jiajie; Hu, Qiaoling; Zhao, Shifang; Shen, Jiacong

2009-07-01

"Micelle-enhanced" polyelectrolyte capsules were fabricated via a layer-by-layer technique, templated on hybrid calcium carbonate particles with built-in polymeric micelles based on polystyrene-b-poly(acrylic acid). Due to the presence of a large number of negatively charged micelles inside the polyelectrolyte capsule, which were liberated from templates, the capsule wall was reconstructed and had properties different to those of conventional polyelectrolyte capsules. This type of capsule could selectively entrap positively charged water-soluble substances. The encapsulation efficiency of positively charged substances was dependent on their molecular weight or size. For some positively charged compounds, such as rhodamine B and lysozyme, the concentration in the capsules was orders of magnitude higher than that in the incubation solution. In addition, in vitro release study suggested that the encapsulated compounds could be released through a sustained manner to a certain degree. All these results point to the fact that these capsules might be used as novel delivery systems for some water-soluble compounds.

Catalytic Micromotors Moving Near Polyelectrolyte-Modified Substrates: The Roles of Surface Charges, Morphology, and Released Ions.

PubMed

Wei, Mengshi; Zhou, Chao; Tang, Jinyao; Wang, Wei

2018-01-24

Synthetic microswimmers, or micromotors, are finding potential uses in a wide range of applications, most of which involve boundaries. However, subtle yet important effects beyond physical confinement on the motor dynamics remain less understood. In this letter, glass substrates were functionalized with positively and negatively charged polyelectrolytes, and the dynamics of micromotors moving close to the modified surfaces was examined. Using acoustic levitation and numerical simulation, we reveal how the speed of a chemically propelled micromotor slows down significantly near a polyelectrolyte-modified surface by the combined effects of surface charges, surface morphology, and ions released from the films.

Aggregation of flexible polyelectrolytes: Phase diagram and dynamics.

PubMed

Tom, Anvy Moly; Rajesh, R; Vemparala, Satyavani

2017-10-14

Similarly charged polymers in solution, known as polyelectrolytes, are known to form aggregated structures in the presence of oppositely charged counterions. Understanding the dependence of the equilibrium phases and the dynamics of the process of aggregation on parameters such as backbone flexibility and charge density of such polymers is crucial for insights into various biological processes which involve biological polyelectrolytes such as protein, DNA, etc. Here, we use large-scale coarse-grained molecular dynamics simulations to obtain the phase diagram of the aggregated structures of flexible charged polymers and characterize the morphology of the aggregates as well as the aggregation dynamics, in the presence of trivalent counterions. Three different phases are observed depending on the charge density: no aggregation, a finite bundle phase where multiple small aggregates coexist with a large aggregate and a fully phase separated phase. We show that the flexibility of the polymer backbone causes strong entanglement between charged polymers leading to additional time scales in the aggregation process. Such slowing down of the aggregation dynamics results in the exponent, characterizing the power law decay of the number of aggregates with time, to be dependent on the charge density of the polymers. These results are contrary to those obtained for rigid polyelectrolytes, emphasizing the role of backbone flexibility.

Effect of dielectric discontinuity on a spherical polyelectrolyte brush

NASA Astrophysics Data System (ADS)

Tergolina, Vinicius B.; dos Santos, Alexandre P.

2017-09-01

In this paper we perform molecular dynamics simulations of a spherical polyelectrolyte brush and counterions in a salt-free medium. The dielectric discontinuity on the grafted nanoparticle surface is taken into account by the method of image charges. Properties of the polyelectrolyte brush are obtained for different parameters, including valency of the counterions, radius of the nanoparticle, and the brush total charge. The monovalent counterions density profiles are obtained and compared with a simple mean-field theoretical approach. The theory allows us to obtain osmotic properties of the system.

Synthesis and characterization of ion containing polymers

NASA Astrophysics Data System (ADS)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 < alpha < 0.6) and counterions (Cl- and I-) were investigated in good solvent (EG, NMF, and GC) and poor solvent (DW and F). The concentration dependence of the specific viscosity and relaxation time of polyelectrolytes in solution agrees with Dobrynin's theoretical predictions at c < c**. Effective charge density greatly impacts the viscosity of polyelectrolyte semidilute solutions, while residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c < 2cs/f. For polyelectrolyte solutions with less condensed counterions, the correlation length obtained from SAXS and rheology perfectly matches and agrees with de Gennes prediction. Dobrynin scaling model successfully predicts the rheology of polyelectrolyte solutions in all cases: without salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

Layer-by-layer self-assembly in the development of electrochemical energy conversion and storage devices from fuel cells to supercapacitors.

PubMed

Xiang, Yan; Lu, Shanfu; Jiang, San Ping

2012-11-07

As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale structures or patterns with excellent functionalities and activities. It has been widely used in the developments of novel materials and nanostructures or patterns from nanotechnologies to medical fields. However, the application of LbL self-assembly in the development of highly efficient electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells (PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this review, the application of LbL self-assembly in the development and synthesis of key materials of PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed. The application of LbL self-assembly for the development of multilayer nanostructured materials for use in electrochemical supercapacitors will also be reviewed and discussed (250 references).

Chain stiffness, salt valency, and concentration influences on titration curves of polyelectrolytes: Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Carnal, Fabrice; Stoll, Serge

2011-01-01

Monte Carlo simulations have been used to study two different models of a weak linear polyelectrolyte surrounded by explicit counterions and salt particles: (i) a rigid rod and (ii) a flexible chain. We focused on the influence of the pH, chain stiffness, salt concentration, and valency on the polyelectrolyte titration process and conformational properties. It is shown that chain acid-base properties and conformational properties are strongly modified when multivalent salt concentration variation ranges below the charge equivalence. Increasing chain stiffness allows to minimize intramolecular electrostatic monomer interactions hence improving the deprotonation process. The presence of di and trivalent salt cations clearly promotes the chain degree of ionization but has only a limited effect at very low salt concentration ranges. Moreover, folded structures of fully charged chains are only observed when multivalent salt at a concentration equal or above charge equivalence is considered. Long-range electrostatic potential is found to influence the distribution of charges along and around the polyelectrolyte backbones hence resulting in a higher degree of ionization and a lower attraction of counterions and salt particles at the chain extremities.

Chain stiffness, salt valency, and concentration influences on titration curves of polyelectrolytes: Monte Carlo simulations.

PubMed

Carnal, Fabrice; Stoll, Serge

2011-01-28

Monte Carlo simulations have been used to study two different models of a weak linear polyelectrolyte surrounded by explicit counterions and salt particles: (i) a rigid rod and (ii) a flexible chain. We focused on the influence of the pH, chain stiffness, salt concentration, and valency on the polyelectrolyte titration process and conformational properties. It is shown that chain acid-base properties and conformational properties are strongly modified when multivalent salt concentration variation ranges below the charge equivalence. Increasing chain stiffness allows to minimize intramolecular electrostatic monomer interactions hence improving the deprotonation process. The presence of di and trivalent salt cations clearly promotes the chain degree of ionization but has only a limited effect at very low salt concentration ranges. Moreover, folded structures of fully charged chains are only observed when multivalent salt at a concentration equal or above charge equivalence is considered. Long-range electrostatic potential is found to influence the distribution of charges along and around the polyelectrolyte backbones hence resulting in a higher degree of ionization and a lower attraction of counterions and salt particles at the chain extremities.

DNA Immobilization and Hybridization Detection by the Intrinsic Molecular Charge Using Capacitive Field-Effect Sensors Modified with a Charged Weak Polyelectrolyte Layer.

PubMed

Bronder, Thomas S; Poghossian, Arshak; Scheja, Sabrina; Wu, Chunsheng; Keusgen, Michael; Mewes, Dieter; Schöning, Michael J

2015-09-16

Miniaturized setup, compatibility with advanced micro- and nanotechnologies, and ability to detect biomolecules by their intrinsic molecular charge favor the semiconductor field-effect platform as one of the most attractive approaches for the development of label-free DNA chips. In this work, a capacitive field-effect EIS (electrolyte-insulator-semiconductor) sensor covered with a layer-by-layer prepared, positively charged weak polyelectrolyte layer of PAH (poly(allylamine hydrochloride)) was used for the label-free electrical detection of DNA (deoxyribonucleic acid) immobilization and hybridization. The negatively charged probe single-stranded DNA (ssDNA) molecules were electrostatically adsorbed onto the positively charged PAH layer, resulting in a preferentially flat orientation of the ssDNA molecules within the Debye length, thus yielding a reduced charge-screening effect and a higher sensor signal. Each sensor-surface modification step (PAH adsorption, probe ssDNA immobilization, hybridization with complementary target DNA (cDNA), reducing an unspecific adsorption by a blocking agent, incubation with noncomplementary DNA (ncDNA) solution) was monitored by means of capacitance-voltage and constant-capacitance measurements. In addition, the surface morphology of the PAH layer was studied by atomic force microscopy and contact-angle measurements. High hybridization signals of 34 and 43 mV were recorded in low-ionic strength solutions of 10 and 1 mM, respectively. In contrast, a small signal of 4 mV was recorded in the case of unspecific adsorption of fully mismatched ncDNA. The density of probe ssDNA and dsDNA molecules as well as the hybridization efficiency was estimated using the experimentally measured DNA immobilization and hybridization signals and a simplified double-layer capacitor model. The results of field-effect experiments were supported by fluorescence measurements, verifying the DNA-immobilization and hybridization event.

Building a road map for tailoring multilayer polyelectrolyte films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ankner, John Francis; Bardoel, Agatha A; Sukishvili, Svetlana

2012-01-01

Researchers are moving a step closer to a definite road map for building layer-by-layer (LbL) assembled polyelectrolyte films, with the assistance of the Liquids Reflectometer at Oak Ridge National Laboratory's Spallation Neutron Source, in Oak Ridge, Tennessee. Scientists using the liquids reflectometer have successfully taken snapshots in close to real time of these multilayered structures for different applications when they modify the structure and function parameters. Polyelecrolytes are polymers that carry charge in aqueous solutions. They contain chemical groups that dissociate in water, making such polymers charged. Most polyelectrolytes are water soluble. They are important components in foods, soaps, shampoos,more » and cosmetics products. They show promise for such environmental work as oil recovery and water treatment. Polyelectrolytes are compelling because researchers can chemically modify how they interact with water for multiple applications. When two types of polyelectrolytes of opposite charge are assembled at a surface in a sequential way using the LbL assembly technique, 'the result is the forming of surface films, useful for coatings, biomedical implants and devices, controlling adhesion of biological molecules, and controlling delivery of therapeutic molecules from surfaces,' said Svetlana Sukhishvili of the Stevens Institute of Technology in New Jersey, the lead chemist on the collaboration. 'Medical doctors often prefer to deliver multiple therapeutic compounds from the coatings in a time-resolved manner,' Sukhishvili said. 'To assist them, material scientists need to learn how to build coatings in which polymer layering will not be compromised when exposed to normal physiological conditions.' 'Being able to control these properties, understanding how what you do to the materials affects their properties, this allows you to apply them to situations where interacting with an environment is very helpful, whether in a biological context or any other kind of water soluble context,' said John Ankner, lead instrument scientist for the Liquids Reflectometer. Ankner said that when several parameters are systematically altered, that allows researchers to map out the whole range of structures in the polymer. 'This work really sets a road map for how to get started with synthesizing polyelectrolyte materials for specific applications. Then, one can say, ok, this methylated material, the one that is 30% charged, is going to be what we want to use for a particular application.' The ORNL collaboration with the Stevens Institute has been conducting a series of experiments at the SNS to study layered film stratification in these polymers. Researchers stitch the polyelectrolyte chains in the LbL films together through what is called ionic pairing and arrange them within fuzzy, ultrathin layers that lie parallel to a solid surface substrate. Exposure of these films to aqueous solutions that contain salt (i.e., conditions that imitate real life) can compromise this film layering, as the salt ions act to weaken the ionic pairing that binds such layers together. So salt solutions are of key interest in studying how to make such layers for use in human applications. In the first research, Ankner, Sukhishvili and her student Li Xu looked at the effects of the layering of two types of LbL films of changing the charge density with a salt solution, and of blocking access to a charged site by nearby groups. The films were composed of positively charged variants of PDMA, a methyl polymer, and PDEA, an ethyl polymer. The other component of both systems is the ion exchanger polystyrene sulfonate (PSS) which features a fixed negative charge. First, a silicon substrate was dipped into solutions of PDMA and PDEA in dilute sodium chloride for a fixed time. Depending on the deposition time and the concentration of the solution, a nanometer-thick monolayer of the polymer adsorbs to the silicon surface. The film buildup is then continued by depositing a layer of PSS, and the cycle is repeated. The PDMA (methyl)/PSS and PDEA (ethyl)/PSS films were then annealed in varying concentrations of aqueous salt solutions. The chemists wanted to know if in these multi-layer cake-like assemblies, the structure can be systematically altered by varying the salt concentration, time in solution, and ultimately other environmental parameters, such as temperature or pH. Neutron reflectivity of the layered films exhibits the quality of the layering, in particular the concentration of the layers and how intermixed they are with adjacent layers. In this research, neutron reflectivity data from films built from 10%, 40%, and 100% charged PDMA or PDEA polyelectrolytes and 100% charged PSS were quantitatively compared to predicted, layered arrangements until the models produced reflectivity patterns matching those of the data.« less

Polyelectrolyte/Graphene Oxide Barrier Film for Flexible OLED.

PubMed

Yang, Seung-Yeol; Park, Jongwhan; Kim, Yong-Seog

2015-10-01

Ultra-thin flexible nano-composite barrier layer consists of graphene oxide and polyelectrolyte was prepared using the layer-by-layer processing method. Microstructures of the barrier layer was optimized via modifying coating conditions and inducing chemical reactions. Although the barrier layer consists of hydrophilic polyelectrolyte was not effective in blocking the water vapor permeation, the chemical reduction of graphene oxide as well as conversion of polyelectrolyte to hydrophobic nature were very effective in reducing the permeation.

Formation, Structure and Electrochemical Impedance Analysis of Microporous Polyelectrolyte Multilayers

NASA Astrophysics Data System (ADS)

Lutkenhaus, Jodie; McEnnis, Kathleen; Hammond, Paula

2007-03-01

Microporous networks are of interest as electrolyte materials, gas separation membranes and catalytic nanoparticle templates. Here, we create microporous polyelectrolyte networks of tunable pore size and connectivity using the layer-by-layer (LBL) technique. In this method, a film is formed from the alternate adsorption of oppositely charged polyelectrolytes from aqueous solution to create a cohesive thin film. Using poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA), LBL thin films of variable composition and charge density were assembled; then, the films were treated in an acidic bath, which ionizes PEI and de-ionizes PAA. This shift in charge density induces morphological rearrangement realized by a microporous network. Depending on the assembly pH and acidic bath pH, we are able to precisely tune the morphology, which is characterized by atomic force microscopy and scanning electron microscopy. To demonstrate the porous nature of the polyelectrolyte multilayer, the pores were filled with non-aqueous electrolyte (i.e. ethylene carbonate, dimethyl carbonate and lithium hexafluorophosphate) and probed with electrochemical impedance spectroscopy. These microporous networks exhibited two time constants, indicative of ions traveling through the liquid-filled pores and ions traveling through the polyelectrolyte matrix.

Weak polyelectrolyte complexation driven by associative charging.

PubMed

Rathee, Vikramjit S; Zervoudakis, Aristotle J; Sidky, Hythem; Sikora, Benjamin J; Whitmer, Jonathan K

2018-03-21

Weak polyelectrolytes are relevant for a wide range of fields; in particular, they have been investigated as "smart" materials for chemical separations and drug delivery. The charges on weak polyelectrolytes are dynamic, causing polymer chains to adopt different equilibrium conformations even with relatively small changes to the surrounding environment. Currently, there exists no comprehensive picture of this behavior, particularly where polymer-polymer interactions have the potential to affect charging properties significantly. In this study, we elucidate the novel interplay between weak polyelectrolyte charging and complexation behavior through coupled molecular dynamics and Monte Carlo simulations. Specifically, we investigate a model of two equal-length and oppositely charging polymer chains in an implicit salt solution represented through Debye-Hückel interactions. The charging tendency of each chain, along with the salt concentration, is varied to determine the existence and extent of cooperativity in charging and complexation. Strong cooperation in the charging of these chains is observed at large Debye lengths, corresponding to low salt concentrations, while at lower Debye lengths (higher salt concentrations), the chains behave in apparent isolation. When the electrostatic coupling is long-ranged, we find that a highly charged chain strongly promotes the charging of its partner chain, even if the environment is unfavorable for an isolated version of that partner chain. Evidence of this phenomenon is supported by a drop in the potential energy of the system, which does not occur at the lower Debye lengths where both potential energies and charge fractions converge for all partner chain charging tendencies. The discovery of this cooperation will be helpful in developing "smart" drug delivery mechanisms by allowing for better predictions for the dissociation point of delivery complexes.

Weak polyelectrolyte complexation driven by associative charging

NASA Astrophysics Data System (ADS)

Rathee, Vikramjit S.; Zervoudakis, Aristotle J.; Sidky, Hythem; Sikora, Benjamin J.; Whitmer, Jonathan K.

2018-03-01

Weak polyelectrolytes are relevant for a wide range of fields; in particular, they have been investigated as "smart" materials for chemical separations and drug delivery. The charges on weak polyelectrolytes are dynamic, causing polymer chains to adopt different equilibrium conformations even with relatively small changes to the surrounding environment. Currently, there exists no comprehensive picture of this behavior, particularly where polymer-polymer interactions have the potential to affect charging properties significantly. In this study, we elucidate the novel interplay between weak polyelectrolyte charging and complexation behavior through coupled molecular dynamics and Monte Carlo simulations. Specifically, we investigate a model of two equal-length and oppositely charging polymer chains in an implicit salt solution represented through Debye-Hückel interactions. The charging tendency of each chain, along with the salt concentration, is varied to determine the existence and extent of cooperativity in charging and complexation. Strong cooperation in the charging of these chains is observed at large Debye lengths, corresponding to low salt concentrations, while at lower Debye lengths (higher salt concentrations), the chains behave in apparent isolation. When the electrostatic coupling is long-ranged, we find that a highly charged chain strongly promotes the charging of its partner chain, even if the environment is unfavorable for an isolated version of that partner chain. Evidence of this phenomenon is supported by a drop in the potential energy of the system, which does not occur at the lower Debye lengths where both potential energies and charge fractions converge for all partner chain charging tendencies. The discovery of this cooperation will be helpful in developing "smart" drug delivery mechanisms by allowing for better predictions for the dissociation point of delivery complexes.

Counterion adsorption theory of dilute polyelectrolyte solutions: Apparent molecular weight, second virial coefficient, and intermolecular structure factor

PubMed Central

Muthukumar, M.

2012-01-01

Polyelectrolyte chains are well known to be strongly correlated even in extremely dilute solutions in the absence of additional strong electrolytes. Such correlations result in severe difficulties in interpreting light scattering measurements in the determination of the molecular weight, radius of gyration, and the second virial coefficient of charged macromolecules at lower ionic strengths from added strong electrolytes. By accounting for charge-regularization of the polyelectrolyte by the counterions, we present a theory of the apparent molecular weight, second virial coefficient, and the intermolecular structure factor in dilute polyelectrolyte solutions in terms of concentrations of the polymer and the added strong electrolyte. The counterion adsorption of the polyelectrolyte chains to differing levels at different concentrations of the strong electrolyte can lead to even an order of magnitude discrepancy in the molecular weight inferred from light scattering measurements. Based on counterion-mediated charge regularization, the second virial coefficient of the polyelectrolyte and the interchain structure factor are derived self-consistently. The effect of the interchain correlations, dominating at lower salt concentrations, on the inference of the radius of gyration and on molecular weight is derived. Conditions for the onset of nonmonotonic scattering wave vector dependence of scattered intensity upon lowering the electrolyte concentration and interpretation of the apparent radius of gyration are derived in terms of the counterion adsorption mechanism. PMID:22830728

Thermodynamic model for polyelectrolyte hydrogels.

PubMed

Arndt, Markus C; Sadowski, Gabriele

2014-09-04

The composition and swelling behavior of hydrogels may be dramatically influenced by external stimuli. Polyelectrolyte hydrogels consisting of charged polymers are particularly well-known for a high sensitivity to the presence of ionic species. For a thermodynamic description of such systems, the polyelectrolyte Perturbed-Chain Statistical Association Fluid Theory (pePC-SAFT) equation of state was augmented and merged with an extension of the modeling of hydrogels. This combined approach allowed for two effects to be taken into account: first, charges along the polymer chain and their interaction with mobile ions of the same or opposite charge in aqueous solutions and, second, the elastic interactions of swellable networks and their effect on Helmholtz energy and pressure. Thus, predictions of the degree of counterion condensation on the polymer chains could be made both for vapor-liquid equilibria of aqueous polyelectrolyte solutions and for polyelectrolyte hydrogels in aqueous salt solutions. The influence of temperature and molecular weight thereon was predicted successfully, and the impact of the degree of neutralization and the effect of additional salts were examined in comparison to literature data. With the inclusion of the influence of the Donnan potential, our model gave good predictions of swellable polyelectrolyte hydrogel systems in salt solutions. Poly(acrylic acid) and poly(methacrylic acid) gels were studied along with their corresponding sodium salts. Their swelling behavior in aqueous NaCl and NaNO3 solutions was examined.

Interplay of polyelectrolytes with different adsorbing surfaces

NASA Astrophysics Data System (ADS)

Xie, Feng

We study the adsorption of polyelectrolytes from solution onto different adsorbing surfaces, focusing on the electrostatic interactions. Measurements of the surface excess, fractional ionization of chargeable groups, segmental orientation, and adsorption kinetics were made using Fourier transform infrared spectroscopy in the mode of attenuated total reflection. Different adsorbing surfaces, from single solid surfaces, solid surfaces modified with adsorbed polymer layer, to fluid-like surfaces-biomembranes were adopted. Both atomic force microscopy (AFM) and fluorescent techniques were employed to investigate the fluid-like surfaces in the absence and in the presence of polyelectrolytes. The work focuses on three primary issues: (i) the charge regulation of weak polyelectrolytes on both homogeneous and heterogeneous surfaces, (ii) the dynamics of adsorption when the surface possesses reciprocal mobility, i.e., biomembrane surface, and (iii) the structural and dynamical properties of the fluid-like surfaces interacting with polyelectrolytes. We find that the ionization of chargeable groups in weak polyelectrolytes is controlled by the charge balance between the adsorbates and the surfaces. A new interpretation of ionization in the adsorbed layer provides a new insight into the fundamental problem of whether ions of opposite charge associate or remain separate. Bjerrum length is found to be a criterion for the onset of surface ionization suppression, which helps to predict and control the conformation transition of proteins. In addition to the effect of different surfaces on the adsorption behavior of polyelectrolytes, we also focused on the response of the surfaces to the adsorbates. Chains that encountered sparsely-covered surfaces spread to maximize the number of segment-surface contacts at rates independent of the molar mass. Surface reconstruction rather than molar mass of the adsorbing molecules appeared to determine the rate of spreading. This contrasts starkly with traditional polymer adsorption onto surfaces whose structure is "frozen" and unresponsive. Finally, preliminary studies on dynamical properties of biomembrane surfaces interacting with polyelectrolytes are presented, using fluorescence correlation spectroscopy (FCS). The significance is to characterize domains induced by polyelectrolyte binding.

Polypeptide multilayer film co-delivers oppositely-charged drug molecules in sustained manners.

PubMed

Jiang, Bingbing; Defusco, Elizabeth; Li, Bingyun

2010-12-13

The current state-of-the-art for drug-carrying biomedical devices is mostly limited to those that release a single drug. Yet there are many situations in which more than one therapeutic agent is needed. Also, most polyelectrolyte multilayer films intended for drug delivery are loaded with active molecules only during multilayer film preparation. In this paper, we present the integration of capsules as vehicles within polypeptide multilayer films for sustained release of multiple oppositely charged drug molecules using layer-by-layer nanoassembly technology. Calcium carbonate (CaCO(3)) particles were impregnated with polyelectrolytes, shelled with polyelectrolyte multilayers, and then assembled onto polypeptide multilayer films using glutaraldehyde. Capsule-integrated polypeptide multilayer films were obtained after decomposition of CaCO(3) templates. Two oppositely charged drugs were loaded into capsules within polypeptide multilayer films postpreparation based on electrostatic interactions between the drugs and the polyelectrolytes impregnated within capsules. We determined that the developed innovative capsule-integrated polypeptide multilayer films could be used to load multiple drugs of very different properties (e.g., opposite charges) any time postpreparation (e.g., minutes before surgical implantation inside an operating room), and such capsule-integrated films allowed simultaneous delivery of two oppositely charged drug molecules and a sustained (up to two weeks or longer) and sequential release was achieved.

Polypeptide Multilayer Film Co-Delivers Oppositely-Charged Drug Molecules in Sustained Manners

PubMed Central

Jiang, Bingbing; DeFusco, Elizabeth; Li, Bingyun

2010-01-01

The current state-of-the-art for drug-carrying biomedical devices is mostly limited to those that release a single drug. Yet there are many situations in which more than one therapeutic agent is needed. Also, most polyelectrolyte multilayer films intending for drug delivery are loaded with active molecules only during multilayer film preparation. In this paper, we present the integration of capsules as vehicles within polypeptide multilayer films for sustained release of multiple oppositely-charged drug molecules using layer-by-layer nanoassembly technology. Calcium carbonate (CaCO3) particles were impregnated with polyelectrolytes, shelled with polyelectrolyte multilayers, and then assembled onto polypeptide multilayer films using glutaraldehyde. Capsule-integrated polypeptide multilayer films were obtained after decomposition of CaCO3 templates. Two oppositely-charged drugs were loaded into capsules within polypeptide multilayer films post-preparation based on electrostatic interactions between the drugs and the polyelectrolytes impregnated within capsules. We determined that the developed innovative capsule-integrated polypeptide multilayer films could be used to load multiple drugs of very different properties (e.g. opposite charges) any time post-preparation (e.g. minutes before surgical implantation inside an operating room), and such capsule-integrated films allowed simultaneous delivery of two oppositely-charged drug molecules and a sustained (up to two weeks or longer) and sequential release was achieved. PMID:21058719

Synthesis of size-controlled acid-resistant hybrid calcium carbonate microparticles as templates for fabricating "micelles-enhanced" polyelectrolyte capsules by the LBL technique.

PubMed

Li, Xiaodong; Hu, Qiaoling; Yue, Linhai; Shen, Jiacong

2006-07-24

Size-controlled, low-dispersed calcium carbonate microparticles were synthesized in the presence of the amphiphilic block copolymer polystyrene-b-poly(acrylic acid) (PS-b-PAA) by modulating the concentration of block copolymer in the reactive system. This type of hybrid microparticles have acid-resistant properties. By investigating the aggregation behaviors of PS-b-PAA micelles by transmission electron microscopy (TEM), the mechanism of hybrid calcium carbonate formation illustrated that the block copolymer served not only as "pseudonuclei" for the growth of calcium carbonate nanocrystals, but also forms the supramicelle congeries, a spherical framework, as templates for calcium carbonate nanocrystal growth into hybrid CaCO(3) particles. Moreover, this pilot study shows that the hybrid microparticle is a novel candidate as a template for fabricating multilayer polyelectrolyte capsules, in which the block copolymer is retained within the capsule interior after core removal under soft conditions. This not only facilitates the encapsulation of special materials, but also provides "micelles-enhanced" polyelectrolyte capsules.

Stability of foam films of oppositely charged polyelectrolyte/surfactant mixtures: effect of isoelectric point.

PubMed

Kristen-Hochrein, Nora; Laschewsky, André; Miller, Reinhard; von Klitzing, Regine

2011-12-15

In the present paper, the influence of the surfactant concentration and the degree of charge of a polymer on foam film properties of oppositely charged polyelectrolyte/surfactant mixtures has been investigated. To verify the assumption that the position of the isoelectric point (IEP) does not change the character of the foam film stabilities, the position of the IEP of the polyelectrolyte/surfactant mixtures has been shifted in two different ways. Within the first series of experiments, the foam film properties were studied using a fixed surfactant concentration of 3 × 10(-5) M in the mixture. Due to the low surfactant concentration, this is a rather dilute system. In the second approach, a copolymer of nonionic and ionic monomer units was used to lower the charge density of the polymer. This gave rise to additional interactions between the polyelectrolyte and the surfactant, which makes the description of the foam film behavior more complex. In both systems, the same characteristics of the foam film stabilities were found: The foam film stability is reduced toward the IEP of the system, followed by a destabilization around the IEP. At polyelectrolyte concentrations above the IEP, foam films are very stable. However, the concentration range where unstable films were formed was rather broad, and the mechanisms leading to the destabilization had different origins. The results were compared with former findings on PAMPS/C(14)TAB mixtures with an IEP of 10(-4) M.

Monte Carlo simulation and equation of state for flexible charged hard-sphere chain fluids: polyampholyte and polyelectrolyte solutions.

PubMed

Jiang, Hao; Adidharma, Hertanto

2014-11-07

The thermodynamic modeling of flexible charged hard-sphere chains representing polyampholyte or polyelectrolyte molecules in solution is considered. The excess Helmholtz energy and osmotic coefficients of solutions containing short polyampholyte and the osmotic coefficients of solutions containing short polyelectrolytes are determined by performing canonical and isobaric-isothermal Monte Carlo simulations. A new equation of state based on the thermodynamic perturbation theory is also proposed for flexible charged hard-sphere chains. For the modeling of such chains, the use of solely the structure information of monomer fluid for calculating the chain contribution is found to be insufficient and more detailed structure information must therefore be considered. Two approaches, i.e., the dimer and dimer-monomer approaches, are explored to obtain the contribution of the chain formation to the Helmholtz energy. By comparing with the simulation results, the equation of state with either the dimer or dimer-monomer approach accurately predicts the excess Helmholtz energy and osmotic coefficients of polyampholyte and polyelectrolyte solutions except at very low density. It also well captures the effect of temperature on the thermodynamic properties of these solutions.

Formation and stability of water-soluble, molecular polyelectrolyte complexes: effects of charge density, mixing ratio, and polyelectrolyte concentration.

PubMed

Shovsky, Alexander; Varga, Imre; Makuska, Ricardas; Claesson, Per M

2009-06-02

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC's are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Polyelectrolyte assisted charge titration spectrometry: Applications to latex and oxide nanoparticles.

PubMed

Mousseau, F; Vitorazi, L; Herrmann, L; Mornet, S; Berret, J-F

2016-08-01

The electrostatic charge density of particles is of paramount importance for the control of the dispersion stability. Conventional methods use potentiometric, conductometric or turbidity titration but require large amount of samples. Here we report a simple and cost-effective method called polyelectrolyte assisted charge titration spectrometry or PACTS. The technique takes advantage of the propensity of oppositely charged polymers and particles to assemble upon mixing, leading to aggregation or phase separation. The mixed dispersions exhibit a maximum in light scattering as a function of the volumetric ratio X, and the peak position XMax is linked to the particle charge density according to σ∼D0XMax where D0 is the particle diameter. The PACTS is successfully applied to organic latex, aluminum and silicon oxide particles of positive or negative charge using poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). The protocol is also optimized with respect to important parameters such as pH and concentration, and to the polyelectrolyte molecular weight. The advantages of the PACTS technique are that it requires minute amounts of sample and that it is suitable to a broad variety of charged nano-objects. Copyright © 2016 Elsevier Inc. All rights reserved.

Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers.

PubMed

Eronen, Paula; Laine, Janne; Ruokolainen, Janne; Osterberg, Monika

2012-05-01

The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC. Copyright © 2011 Elsevier Inc. All rights reserved.

Lipid Layers on Polyelectrolyte Multilayers: Understanding Lipid-Polyelectrolyte Interactions and Applications on the Surface Engineering of Nanomaterials.

PubMed

Diamanti, Eleftheria; Gregurec, Danijela; Gabriela, Romero; Cuellar, J L; Donath, E; Moya, S E

2016-06-01

In this manuscript we review work of our group on the assembly of lipid layers on top of polyelectrolyte multilayers (PEMs). The assembly of lipid layers with zwitterionic and charged lipids on PEMs is studied as a function of lipid and polyelectrolyte composition by the Quartz Crystal Microbalance. Polyelectrolyte lipid interactions are studied by means of Atomic Force Spectroscopy. We also show the coating of lipid layers for engineering different nanomaterials, i.e., carbon nanotubes and poly(lactic-co-glycolic) nanoparticles and how these can be used to decrease in vitro toxicity and to direct the intracellular localization of nanomaterials.

Physical deposition behavior of stiff amphiphilic polyelectrolytes in an external electric field

NASA Astrophysics Data System (ADS)

Hu, Dongmei; Zuo, Chuncheng; Cao, Qianqian; Chen, Hongli

2017-08-01

Coarse-grained molecular dynamics simulations are conducted to study the physical deposition behavior of stiff amphiphilic polyelectrolytes (APEs) in an external electric field. The effects of chain stiffness, the charge distribution of a hydrophilic block, and electric field strength are investigated. Amphiphilic multilayers, which consist of a monolayer of adsorbed hydrophilic monomers (HLMs), a hydrophobic layer, and another hydrophilic layer, are formed in a selective solvent. All cases exhibit locally ordered hydrophilic monolayers. Two kinds of hydrophobic micelles are distinguished based on local structures. Stripe and network hydrophobic patterns are formed in individual cases. Increasing the chain stiffness decreases the thickness of the deposited layer, the lateral size of the hydrophobic micelles, and the amount of deposition. Increasing the number of positively charged HLMs in a single chain has the same effect as increasing chain stiffness. Moreover, when applied normally to the substrate, the electric field compresses the deposited structures and increases the amount of deposition by pulling more PEs toward the substrate. A stronger electric field also facilitates the formation of a thinner and more ordered hydrophilic adsorption layer. These estimates help us explore how to tailor patterned nano-surfaces, nano-interfaces, or amphiphilic nanostructures by physically depositing semi-flexible APEs which is of crucial importance in physical sciences, life sciences and nanotechnology.

Scaling Theory of Polyelectrolyte Nanogels

NASA Astrophysics Data System (ADS)

Qu, Li-Jian

2017-08-01

The present paper develops the scaling theory of polyelectrolyte nanogels in dilute and semidilute solutions. The dependencies of the nanogel dimension on branching topology, charge fraction, subchain length, segment number, solution concentration are obtained. For a single polyelectrolyte nanogel in salt free solution, the nanogel may be swelled by the Coulombic repulsion (the so-called polyelectrolyte regime) or the osmotic counterion pressure (the so-called osmotic regime). Characteristics and boundaries between different regimes of a single polyelectrolyte nanogel are summarized. In dilute solution, the nanogels in polyelectrolyte regime will distribute orderly with the increase of concentration. While the nanogels in osmotic regime will always distribute randomly. Different concentration dependencies of the size of a nanogel in polyelectrolyte regime and in osmotic regime are also explored. Supported by China Earthquake Administration under Grant No. 20150112 and National Natural Science Foundation of China under Grant No. 21504014

Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores

PubMed Central

Han, Ji-Hyung; Khoo, Edwin; Bai, Peng; Bazant, Martin Z.

2014-01-01

Understanding over-limiting current (faster than diffusion) is a long-standing challenge in electrochemistry with applications in desalination and energy storage. Known mechanisms involve either chemical or hydrodynamic instabilities in unconfined electrolytes. Here, it is shown that over-limiting current can be sustained by surface conduction in nanopores, without any such instabilities, and used to control dendritic growth during electrodeposition. Copper electrodeposits are grown in anodized aluminum oxide membranes with polyelectrolyte coatings to modify the surface charge. At low currents, uniform electroplating occurs, unaffected by surface modification due to thin electric double layers, but the morphology changes dramatically above the limiting current. With negative surface charge, growth is enhanced along the nanopore surfaces, forming surface dendrites and nanotubes behind a deionization shock. With positive surface charge, dendrites avoid the surfaces and are either guided along the nanopore centers or blocked from penetrating the membrane. PMID:25394685

Novel polyelectrolyte complex based carbon nanotube composite architectures

NASA Astrophysics Data System (ADS)

Razdan, Sandeep

This study focuses on creating novel architectures of carbon nanotubes using polyelectrolytes. Polyelectrolytes are unique polymers possessing resident charges on the macromolecular chains. This property, along with their biocompatibility (true for most polymers used in this study) makes them ideal candidates for a variety of applications such as membranes, drug delivery systems, scaffold materials etc. Carbon nanotubes are also unique one-dimensional nanoscale materials that possess excellent electrical, mechanical and thermal properties owing to their small size, high aspect ratio, graphitic structure and strength arising from purely covalent bonds in the molecular structure. The present study tries to investigate the synthesis processes and material properties of carbon nanotube composites comprising of polyelectrolyte complexes. Carbon nanotubes are dispersed in a polyelectrolyte and are induced into taking part in a complexation process with two oppositely charged polyelectrolytes. The resulting stoichiometric precipitate is then drawn into fiber form and dried as such. The material properties of the carbon nanotube fibers were characterized and related to synthesis parameters and material interactions. Also, an effort was made to understand and predict fiber morphology resulting from the complexation and drawing process. The study helps to delineate the synthesis and properties of the said polyelectrolyte complex-carbon nanotube architectures and highlights useful properties, such as electrical conductivity and mechanical strength, which could make these structures promising candidates for a variety of applications.

Formation of polyelectrolyte complexes with diethylaminoethyl dextran: charge ratio and molar mass effect.

PubMed

Le Cerf, Didier; Pepin, Anne Sophie; Niang, Pape Momar; Cristea, Mariana; Karakasyan-Dia, Carole; Picton, Luc

2014-11-26

The formation of polyelectrolyte complexes (PECs) between carboxymethyl pullulan and DEAE Dextran, was investigated, in dilute solution, with emphasis on the effect of charge density (molar ratio or pH) and molar masses. Electrophoretic mobility measurements have evidenced that insoluble PECs (neutral electrophoretic mobility) occurs for charge ratio between 0.6 (excess of polycation) and 1 (stoichiometry usual value) according to the pH. This atypical result is explained by the inaccessibility of some permanent cationic charge when screened by pH dependant cationic ones (due to the Hoffman alkylation). Isothermal titration calorimetry (ITC) indicates an endothermic formation of PEC with a binding constant around 10(5) L mol(-1). Finally asymmetrical flow field flow fractionation coupled on line with static multi angle light scattering (AF4/MALS) evidences soluble PECs with very large average molar masses and size around 100 nm, in agreement with scrambled eggs multi-association between various polyelectrolyte chains. Copyright © 2014 Elsevier Ltd. All rights reserved.

Counterion adsorption and desorption rate of a charged macromolecule

NASA Astrophysics Data System (ADS)

Shi, Yu; Yang, Jingfa; Zhao, Jiang

The rate constant of counterion adsorption to and desorption from a synthetic polyelectrolyte, polystyrene sulfonate (PSS-), is measured in aqueous solution by single molecule fluorescence spectroscopy. The results show that both adsorption and desorption rate of counterions have strong dependence on polymer concentration, salt concentration as well as the molecular weight of polyelectrolytes. The results clearly demonstrate that the contribution of electrostatic interaction and the translational entropy to the distribution of counterions of a polyelectrolyte molecule. The information is helpful to the understanding of polyelectrolyte physics. National Natural Science Foundation of China.

Complexation behavior of oppositely charged polyelectrolytes: Effect of charge distribution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Mingtian; Li, Baohui, E-mail: dliang@pku.edu.cn, E-mail: baohui@nankai.edu.cn; Zhou, Jihan

Complexation behavior of oppositely charged polyelectrolytes in a solution is investigated using a combination of computer simulations and experiments, focusing on the influence of polyelectrolyte charge distributions along the chains on the structure of the polyelectrolyte complexes. The simulations are performed using Monte Carlo with the replica-exchange algorithm for three model systems where each system is composed of a mixture of two types of oppositely charged model polyelectrolyte chains (EGEG){sub 5}/(KGKG){sub 5}, (EEGG){sub 5}/(KKGG){sub 5}, and (EEGG){sub 5}/(KGKG){sub 5}, in a solution including explicit solvent molecules. Among the three model systems, only the charge distributions along the chains are notmore » identical. Thermodynamic quantities are calculated as a function of temperature (or ionic strength), and the microscopic structures of complexes are examined. It is found that the three systems have different transition temperatures, and form complexes with different sizes, structures, and densities at a given temperature. Complex microscopic structures with an alternating arrangement of one monolayer of E/K monomers and one monolayer of G monomers, with one bilayer of E and K monomers and one bilayer of G monomers, and with a mixture of monolayer and bilayer of E/K monomers in a box shape and a trilayer of G monomers inside the box are obtained for the three mixture systems, respectively. The experiments are carried out for three systems where each is composed of a mixture of two types of oppositely charged peptide chains. Each peptide chain is composed of Lysine (K) and glycine (G) or glutamate (E) and G, in solution, and the chain length and amino acid sequences, and hence the charge distribution, are precisely controlled, and all of them are identical with those for the corresponding model chain. The complexation behavior and complex structures are characterized through laser light scattering and atomic force microscopy measurements. The order of the apparent weight-averaged molar mass and the order of density of complexes observed from the three experimental systems are qualitatively in agreement with those predicted from the simulations.« less

Electro-osmotic flow of semidilute polyelectrolyte solutions.

PubMed

Uematsu, Yuki; Araki, Takeaki

2013-09-07

We investigate electro-osmosis in aqueous solutions of polyelectrolytes using mean-field equations. A solution of positively charged polyelectrolytes is confined between two negatively charged planar surfaces, and an electric field is applied parallel to the surfaces. When electrostatic attraction between the polymer and the surface is strong, the polymers adhere to the surface, forming a highly viscous adsorption layer that greatly suppresses the electro-osmosis. Conversely, electro-osmosis is enhanced by depleting the polymers from the surfaces. We also found that the electro-osmotic flow is invertible when the electrostatic potential decays to its bulk value with the opposite sign. These behaviors are well explained by a simple mathematical form of the electro-osmotic coefficient.

Osmotic and Salted Brush Phase of Polyelectrolyte Brushes

NASA Astrophysics Data System (ADS)

Helm, Christane A.; Ahrens, Heiko; Förster, Stephan

2004-03-01

Amphiphilic block copolymers consisting of a fluid hydrophobic Poly(ethyletylene) (PEE), and a Poly(styrenesulfonate) (PSS) part form monolayers at the air/water interface. With x-ray reflectivity it is shown that the hydrophobic blocks of PEE_114PSS_83 and PEE_144PSS_136 constitute a nm-thick melt, while the polyelectrolyte forms an osmotically swollen brush with counterion incorporation. A slight thickness increase on monolayer compression is found which can be explained by the strong stretching of the brushes. Only at high salt conditions (above 0.1 M), the brush shrinks and the thickness scales with the molecular area (exponent -1/3), and with the salt concentration (exponent ca. -1/5). With Grazing Incidence Diffraction, the lateral order of the polyelectrolyte chains can be detected.

Casein Aggregates Built Step-by-Step on Charged Polyelectrolyte Film Surfaces Are Calcium Phosphate-cemented*

PubMed Central

Nagy, Krisztina; Pilbat, Ana-Maria; Groma, Géza; Szalontai, Balázs; Cuisinier, Frédéric J. G.

2010-01-01

The possible mechanism of casein aggregation and micelle buildup was studied in a new approach by letting α-casein adsorb from low concentration (0.1 mg·ml−1) solutions onto the charged surfaces of polyelectrolyte films. It was found that α-casein could adsorb onto both positively and negatively charged surfaces. However, only when its negative phosphoseryl clusters remained free, i.e. when it adsorbed onto a negative surface, could calcium phosphate (CaP) nanoclusters bind to the casein molecules. Once the CaP clusters were in place, step-by-step building of multilayered casein architectures became possible. The presence of CaP was essential; neither Ca2+ nor phosphate could alone facilitate casein aggregation. Thus, it seems that CaP is the organizing motive in the casein micelle formation. Atomic force microscopy revealed that even a single adsorbed casein layer was composed of very small (in the range of tens of nanometers) spherical forms. The stiffness of the adsorbed casein layer largely increased in the presence of CaP. On this basis, we can imagine that casein micelles emerge according to the following scheme. The amphipathic casein monomers aggregate into oligomers via hydrophobic interactions even in the absence of CaP. Full scale, CaP-carrying micelles could materialize by interlocking these casein oligomers with CaP nanoclusters. Such a mechanism would not contradict former experimental results and could offer a synthesis between the submicelle and the block copolymer models of casein micelles. PMID:20921229

Assembly of purple membranes on polyelectrolyte films.

PubMed

Saab, Marie-belle; Estephan, Elias; Cloitre, Thierry; Legros, René; Cuisinier, Frédéric J G; Zimányi, László; Gergely, Csilla

2009-05-05

The membrane protein bacteriorhodopsin in its native membrane bound form (purple membrane) was adsorbed and incorporated into polyelectrolyte multilayered films, and adsorption was in situ monitored by optical waveguide light-mode spectroscopy. The formation of a single layer or a double layer of purple membranes was observed when adsorbed on negatively or positively charged surfaces, respectively. The purple membrane patches adsorbed on the polyelectrolyte multilayers were also evidenced by atomic force microscopy images. The driving forces of the adsorption process were evaluated by varying the ionic strength of the solution as well as the purple membrane concentration. At high purple membrane concentration, interpenetrating polyelectrolyte loops might provide new binding sites for the adsorption of a second layer of purple membranes, whereas at lower concentrations only a single layer is formed. Negative surfaces do not promote a second protein layer adsorption. Driving forces other than just electrostatic ones, such as hydrophobic forces, should play a role in the polyelectrolyte/purple membrane layering. The subtle interplay of all these factors determines the formation of the polyelectrolyte/purple membrane matrix with a presumably high degree of orientation for the incorporated purple membranes, with their cytoplasmic, or extracellular side toward the bulk on negatively or positively charged polyelectrolyte, respectively. The structural stability of bacteriorhodopsin during adsorption onto the surface and incorporation into the polyelectrolyte multilayers was investigated by Fourier transform infrared spectroscopy in attenuated total reflection mode. Adsorption and incorporation of purple membranes within polyelectrolyte multilayers does not disturb the conformational majority of membrane-embedded alpha-helix structures of the protein, but may slightly alter the structure of the extramembraneous segments or their interaction with the environment. This high stability is different from the lower stability of the predominantly beta-sheet structures of numerous globular proteins when adsorbed onto surfaces.

Phase behaviour and structure of stable complexes of oppositely charged polyelectrolytes

NASA Astrophysics Data System (ADS)

Mengarelli, V.; Auvray, L.; Zeghal, M.

2009-03-01

We study the formation and structure of stable electrostatic complexes between oppositely charged polyelectrolytes, a long polymethacrylic acid and a shorter polyethylenimine, at low pH, where the polyacid is weakly charged. We explore the phase diagram as a function of the charge and concentration ratio of the constituents. In agreement with theory, turbidity and ζ potential measurements show two distinct regimes of weak and strong complexation, which appear successively as the pH is increased and are separated by a well-defined limit. Weak complexes observed by neutron scattering and contrast matching have an open, non-compact structure, while strong complexes are condensed.

Diffusion of Sites versus Polymers in Polyelectrolyte Complexes and Multilayers.

PubMed

Fares, Hadi M; Schlenoff, Joseph B

2017-10-18

It has long been assumed that the spontaneous formation of materials such as complexes and multilayers from charged polymers depends on (inter)diffusion of these polyelectrolytes. Here, we separately examine the mass transport of polymer molecules and extrinsic sites-charged polyelectrolyte repeat units balanced by counterions-within thin films of polyelectrolyte complex, PEC, using sensitive isotopic labeling techniques. The apparent diffusion coefficients of these sites within PEC films of poly(diallyldimethylammonium), PDADMA, and poly(styrenesulfonate), PSS, are at least 2 orders of magnitude faster than the diffusion of polyelectrolytes themselves. This is because site diffusion requires only local rearrangements of polyelectrolyte repeat units, placing far fewer kinetic limitations on the assembly of polyelectrolyte complexes in all of their forms. Site diffusion strongly depends on the salt concentration (ionic strength) of the environment, and diffusion of PDADMA sites is faster than that of PSS sites, accounting for the asymmetric nature of multilayer growth. Site diffusion is responsible for multilayer growth in the linear and into the exponential regimes, which explains how PDADMA can mysteriously "pass through" layers of PSS. Using quantitative relationships between site diffusion coefficient and salt concentration, conditions were identified that allowed the diffusion length to always exceed the film thickness, leading to full exponential growth over 3 orders of magnitude thickness. Both site and polymer diffusion were independent of molecular weight, suggesting that ion pairing density is a limiting factor. Polyelectrolyte complexes are examples of a broader class of dynamic bulk polymeric materials that (self-) assemble via the transport of cross-links or defects rather than actual molecules.

Salt Effects on Surface Structures of Polyelectrolyte Multilayers (PEMs) Investigated by Vibrational Sum Frequency Generation (SFG) Spectroscopy.

PubMed

Ge, Aimin; Matsusaki, Michiya; Qiao, Lin; Akashi, Mitsuru; Ye, Shen

2016-04-26

Sum frequency generation (SFG) vibrational spectroscopy was employed to investigate the surface structures of polyelectrolyte multilayers (PEMs) constructed by sequentially alternating adsorption of poly(diallyldimethylammonium chloride) (PDDA) and poly(styrenesulfonate) (PSS). It was found that the surface structures and surface charge density of the as-deposited PEMs of PDDA/PSS significantly depend on the concentration of sodium chloride (NaCl) present in the polyelectrolyte solutions. Furthermore, it was found that the surface structure of the as-deposited PEMs is in a metastable state and will reach the equilibrium state by diffusion of the polyelectrolyte chain after an aging process, resulting in a polyelectrolyte mixture on the PEM surfaces.

Monte Carlo simulation and equation of state for flexible charged hard-sphere chain fluids: Polyampholyte and polyelectrolyte solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Hao; Adidharma, Hertanto, E-mail: adidharm@uwyo.edu

The thermodynamic modeling of flexible charged hard-sphere chains representing polyampholyte or polyelectrolyte molecules in solution is considered. The excess Helmholtz energy and osmotic coefficients of solutions containing short polyampholyte and the osmotic coefficients of solutions containing short polyelectrolytes are determined by performing canonical and isobaric-isothermal Monte Carlo simulations. A new equation of state based on the thermodynamic perturbation theory is also proposed for flexible charged hard-sphere chains. For the modeling of such chains, the use of solely the structure information of monomer fluid for calculating the chain contribution is found to be insufficient and more detailed structure information must thereforemore » be considered. Two approaches, i.e., the dimer and dimer-monomer approaches, are explored to obtain the contribution of the chain formation to the Helmholtz energy. By comparing with the simulation results, the equation of state with either the dimer or dimer-monomer approach accurately predicts the excess Helmholtz energy and osmotic coefficients of polyampholyte and polyelectrolyte solutions except at very low density. It also well captures the effect of temperature on the thermodynamic properties of these solutions.« less

Brownian Dynamics Simulations of Polyelectrolyte Adsorption in Shear Flow

NASA Astrophysics Data System (ADS)

Panwar, Ajay

2005-03-01

The adsorption of polyelectrolytes onto charged surfaces often occurs in microfludic devices and can influence their operation. We employ Brownian dynamics simulations to investigate the effect of a simple shear flow on the adsorption of an isolated polyelectrolyte molecule onto an oppositely charged surface. The polyelectrolyte is modeled as a freely-jointed bead-rod chain where the total charge is distributed uniformly among all the beads, and the beads are allowed to interact with one another and the charged surface through screened Coulombic interactions. The simulations are performed by placing the chain some distance above the surface, and the adsorption behavior is studied as a function of the screening length. Specifically, we look at the components of the radius of gyration, normal and parallel to the adsorbing surface, as functions of the screening length, both in the absence and presence of the flow. We find that in the absence of flow, the chain lies flat and stretched on the adsorbing surface in the limit of weak screening, but attains free solution behavior in the limit of strong screening. In the presence of a shear flow, the chain orientation in the direction of the flow increases with increasing Weissenberg number over the entire range of screening lengths studied. We also find that increasing the strength of the shear flow leads to an increased contact of the chain with the surface compared to the case when no flow is present.

Development of a robust pH-sensitive polyelectrolyte ionomer complex for anticancer nanocarriers

PubMed Central

Lim, Chaemin; Youn, Yu Seok; Lee, Kyung Soo; Hoang, Ngoc Ha; Sim, Taehoon; Lee, Eun Seong; Oh, Kyung Taek

2016-01-01

A polyelectrolyte ionomer complex (PIC) composed of cationic and anionic polymers was developed for nanomedical applications. Here, a poly(ethylene glycol)–poly(lactic acid)–poly(ethylene imine) triblock copolymer (PEG–PLA–PEI) and a poly(aspartic acid) (P[Asp]) homopolymer were synthesized. These polyelectrolytes formed stable aggregates through electrostatic interactions between the cationic PEI and the anionic P(Asp) blocks. In particular, the addition of a hydrophobic PLA and a hydrophilic PEG to triblock copolyelectrolytes provided colloidal aggregation stability by forming a tight hydrophobic core and steric hindrance on the surface of PIC, respectively. The PIC showed different particle sizes and zeta potentials depending on the ratio of cationic PEI and anionic P(Asp) blocks (C/A ratio). The doxorubicin (dox)-loaded PIC, prepared with a C/A ratio of 8, demonstrated pH-dependent behavior by the deprotonation/protonation of polyelectrolyte blocks. The drug release and the cytotoxicity of the dox-loaded PIC (C/A ratio: 8) increased under acidic conditions compared with physiological pH, due to the destabilization of the formation of the electrostatic core. In vivo animal imaging revealed that the prepared PIC accumulated at the targeted tumor site for 24 hours. Therefore, the prepared pH-sensitive PIC could have considerable potential as a nanomedicinal platform for anticancer therapy. PMID:26955270

Layer-by-Layer Assembled Architecture of Polyelectrolyte Multilayers and Graphene Sheets on Hollow Carbon Spheres/Sulfur Composite for High-Performance Lithium-Sulfur Batteries.

PubMed

Wu, Feng; Li, Jian; Su, Yuefeng; Wang, Jing; Yang, Wen; Li, Ning; Chen, Lai; Chen, Shi; Chen, Renjie; Bao, Liying

2016-09-14

In the present work, polyelectrolyte multilayers (PEMs) and graphene sheets are applied to sequentially coat on the surface of hollow carbon spheres/sulfur composite by a flexible layer-by-layer (LBL) self-assembly strategy. Owing to the strong electrostatic interactions between the opposite charged materials, the coating agents are very stable and the coating procedure is highly efficient. The LBL film shows prominent impact on the stability of the cathode by acting as not only a basic physical barrier, and more importantly, an ion-permselective film to block the polysulfides anions by Coulombic repulsion. Furthermore, the graphene sheets can help to stabilize the polyelectrolytes film and greatly reduce the inner resistance of the electrode by changing the transport of the electrons from a "point-to-point" mode to a more effective "plane-to-point'' mode. On the basis of the synergistic effect of the PEMs and graphene sheets, the fabricated composite electrode exhibits very stable cycling stability for over 200 cycles at 1 A g(-1), along with a high average Coulombic efficiency of 99%. With the advantages of rapid and controllable fabrication of the LBL coating film, the multifunctional architecture developed in this study should inspire the design of other lithium-sulfur cathodes with unique physical and chemical properties.

Salt dependence of compression normal forces of quenched polyelectrolyte brushes

NASA Astrophysics Data System (ADS)

Hernandez-Zapata, Ernesto; Tamashiro, Mario N.; Pincus, Philip A.

2001-03-01

We obtained mean-field expressions for the compression normal forces between two identical opposing quenched polyelectrolyte brushes in the presence of monovalent salt. The brush elasticity is modeled using the entropy of ideal Gaussian chains, while the entropy of the microions and the electrostatic contribution to the grand potential is obtained by solving the non-linear Poisson-Boltzmann equation for the system in contact with a salt reservoir. For the polyelectrolyte brush we considered both a uniformly charged slab as well as an inhomogeneous charge profile obtained using a self-consistent field theory. Using the Derjaguin approximation, we related the planar-geometry results to the realistic two-crossed cylinders experimental set up. Theoretical predictions are compared to experimental measurements(Marc Balastre's abstract, APS March 2001 Meeting.) of the salt dependence of the compression normal forces between two quenched polyelectrolyte brushes formed by the adsorption of diblock copolymers poly(tert-butyl styrene)-sodium poly(styrene sulfonate) [PtBs/NaPSS] onto an octadecyltriethoxysilane (OTE) hydrophobically modified mica, as well as onto bare mica.

Coarse-grained simulations of polyelectrolyte complexes: MARTINI models for poly(styrene sulfonate) and poly(diallyldimethylammonium)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vögele, Martin; Department of Theoretical Biophysics, Max Planck Institute of Biophysics, Frankfurt a. M.; Holm, Christian

2015-12-28

We present simulations of aqueous polyelectrolyte complexes with new MARTINI models for the charged polymers poly(styrene sulfonate) and poly(diallyldimethylammonium). Our coarse-grained polyelectrolyte models allow us to study large length and long time scales with regard to chemical details and thermodynamic properties. The results are compared to the outcomes of previous atomistic molecular dynamics simulations and verify that electrostatic properties are reproduced by our MARTINI coarse-grained approach with reasonable accuracy. Structural similarity between the atomistic and the coarse-grained results is indicated by a comparison between the pair radial distribution functions and the cumulative number of surrounding particles. Our coarse-grained models aremore » able to quantitatively reproduce previous findings like the correct charge compensation mechanism and a reduced dielectric constant of water. These results can be interpreted as the underlying reason for the stability of polyelectrolyte multilayers and complexes and validate the robustness of the proposed models.« less

Segregation in like-charged polyelectrolyte-surfactant mixtures can be precisely tuned via manipulation of the surfactant mass ratio.

PubMed

Wills, Peter W; Lopez, Sonia G; Burr, Jocelyn; Taboada, Pablo; Yeates, Stephen G

2013-04-09

In this study, we consider segregative phase separation in aqueous mixtures of quaternary ammonium surfactants didecyldimethylammonium chloride (DDQ) and alkyl (C12, 70%; C14 30%) dimethyl benzyl ammonium chloride (BAC) upon the addition of poly(diallyldimethylammonium) chloride (pDADMAC) as a function of both concentration and molecular weight. The nature of the surfactant type is dominant in determining the concentration at which separation into an upper essentially surfactant-rich phase and lower polyelectrolyte-rich phase is observed. However, for high-molecular-weight pDADMAC there is a clear indication of an additional depletion flocculation effect. When the BAC/DDQ ratio is tuned, the segregative phase separation point can be precisely controlled. We propose a phase separation mechanism for like-charged quaternary ammonium polyelectrolyte/surfactant/water mixtures induced by a reduction in the ionic atmosphere around the surfactant headgroup and possible ion pair formation. An additional polyelectrolyte-induced depletion flocculation effect was also observed.

Smooth model surfaces from lignin derivatives. II. Adsorption of polyelectrolytes and PECs monitored by QCM-D.

PubMed

Norgren, Magnus; Gärdlund, Linda; Notley, Shannon M; Htun, Myat; Wågberg, Lars

2007-03-27

For the first time to the knowledge of the authors, well-defined and stable lignin model surfaces have been utilized as substrates in polyelectrolyte adsorption studies. The adsorption of polyallylamine (PAH), poly(acrylic acid) (PAA), and polyelectrolyte complexes (PECs) was monitored using quartz crystal microgravimetry with dissipation (QCM-D). The PECs were prepared by mixing PAH and PAA at different ratios and sequences, creating both cationic and anionic PECs with different charge levels. The adsorption experiments were performed in 1 and 10 mM sodium chloride solutions at pH 5 and 7.5. The highest adsorption of PAH and cationic PECs was found at pH 7.5, where the slightly negatively charged nature of the lignin substrate is more pronounced, governing electrostatic attraction of oppositely charged polymeric substances. An increase in the adsorption was further found when the electrolyte concentration was increased. In comparison, both PAA and the anionic PEC showed remarkably high adsorption to the lignin model film. The adsorption of PAA was further studied on silica and was found to be relatively low even at high electrolyte concentrations. This indicated that the high PAA adsorption on the lignin films was not induced by a decreased solubility of the anionic polyelectrolyte. The high levels of adsorption on lignin model surfaces found both for PAA and the anionic PAA-PAH polyelectrolyte complex points to the presence of strong nonionic interactions in these systems.

Kinetics of electrically and chemically induced swelling in polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Grimshaw, P. E.; Nussbaum, J. H.; Grodzinsky, A. J.; Yarmush, M. L.

1990-09-01

Controlled swelling and shrinking of polyelectrolyte gels is useful for regulating the transport of solutes into, out of, and through these materials. A macroscopic continuum model is presented to predict the kinetics of swelling in polyelectrolyte gel membranes induced by augmentation of electrostatic swelling forces arising from membrane fixed charge groups. The model accounts for ionic transport within the membrane, electrodiffusion phenomena, dissociation of membrane charge groups, intramembrane fluid flow, and mechanical deformation of the membrane matrix. Model predictions are compared with measurements of chemically and electrically induced swelling and shrinking in crosslinked polymethacrylic acid (PMAA) membranes. Large, reversible changes in PMAA membrane hydration were observed after changing the bath pH or by applying an electric field to modify the intramembrane ionic environment and fixed charge density. A relatively slow swelling process and more rapid shrinking for both chemical and electrical modulation of the intramembrane pH are observed. The model indicates that retardation of membrane swelling is dominated by diffusion-limited reaction of H+ ions with membrane charge groups, and that the more rapid shrinking is limited primarily by mechanical processes.

Novel polyelectrolytes

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor)

1978-01-01

Cationic polyelectrolytes are formed by the polymerization in absence of oxygen of a monomer of the general formula: ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers. Segments of the linear polymer may be attached to or formed in the presence of polyfunctional reactive tertiary amines or halogen polymeric substrates or polyfunctional lower molecular reactive polyfunctional substrates to form branched or star polyelectrolytes by a quaternization polymerization reaction.

pH Reversible Encapsulation of Oppositely Charged Colloids Mediated by Polyelectrolytes

PubMed Central

2017-01-01

We report the first example of reversible encapsulation of micron-sized particles by oppositely charged submicron smaller colloids. The reversibility of this encapsulation process is regulated by pH-responsive poly(acrylic acid) (PAA) present in solution. The competitive adsorption between the small colloids and the poly(acrylic acid) on the surface of the large colloids plays a key role in the encapsulation behavior of the system. pH offers an experimental knob to tune the electrostatic interactions between the two oppositely charged particle species via regulation of the charge density of the poly(acrylic acid). This results in an increased surface coverage of the large colloids by the smaller colloids when decreasing pH. Furthermore, the poly(acrylic acid) also acts as a steric barrier limiting the strength of the attractive forces between the oppositely charged particle species, thereby enabling detachment of the smaller colloids. Finally, based on the pH tunability of the encapsulation behavior and the ability of the small colloids to detach, reversible encapsulation is achieved by cycling pH in the presence of the PAA polyelectrolytes. The role of polyelectrolytes revealed in this work provides a new and facile strategy to control heteroaggregation behavior between oppositely charged colloids, paving the way to prepare sophisticated hierarchical assemblies. PMID:28419800

Apparent Ionic Charge in Electrolyte and Polyelectrolyte Solutions

ERIC Educational Resources Information Center

Magdelenat, H.; And Others

1978-01-01

Compares average displacements of charged particles under thermal motion alone with those obtained by the action of an external electric field to develop a concept of "apparent charge" to approximate actual structural charge in an electrolyte solution. (SL)

Molecular Structure and Sequence in Complex Coacervates

NASA Astrophysics Data System (ADS)

Sing, Charles; Lytle, Tyler; Madinya, Jason; Radhakrishna, Mithun

Oppositely-charged polyelectrolytes in aqueous solution can undergo associative phase separation, in a process known as complex coacervation. This results in a polyelectrolyte-dense phase (coacervate) and polyelectrolyte-dilute phase (supernatant). There remain challenges in understanding this process, despite a long history in polymer physics. We use Monte Carlo simulation to demonstrate that molecular features (charge spacing, size) play a crucial role in governing the equilibrium in coacervates. We show how these molecular features give rise to strong monomer sequence effects, due to a combination of counterion condensation and correlation effects. We distinguish between structural and sequence-based correlations, which can be designed to tune the phase diagram of coacervation. Sequence effects further inform the physical understanding of coacervation, and provide the basis for new coacervation models that take monomer-level features into account.

Solvation effects on like-charge attraction.

PubMed

Ghanbarian, Shahzad; Rottler, Jörg

2013-02-28

We present results of molecular dynamics simulations of the electrostatic interaction between two parallel charged rods in the presence of divalent counterions. Such polyelectrolytes have been considered as a simple model for understanding electrostatic interactions in highly charged biomolecules such as DNA. Since there are correlations between the free charge carriers, the phenomenon of like charge attraction appears for specific parameters. We explore the role of solvation effects and the resulting deviations from Coulomb's law on the nanoscale on this peculiar phenomenon. The behavior of the force between the charged rods in a simulation with atomistic representation of water molecules is completely different from a model in which water is modeled as a continuum dielectric. By calculating counterion-rodion pair correlation functions, we find that the presence of water molecules changes the structure of the counterion cloud and results in both qualitative and quantitative changes of the force between highly charged polyelectrolytes.

Multifunctional nanoparticulate polyelectrolyte complexes.

PubMed

Hartig, Sean M; Greene, Rachel R; DasGupta, Jayasri; Carlesso, Gianluca; Dikov, Mikhail M; Prokop, Ales; Davidson, Jeffrey M

2007-12-01

Water-soluble, biodegradable, polymeric, polyelectrolyte complex dispersions (PECs) have evolved because of the limitations, in terms of toxicity, of the currently available systems. These aqueous nanoparticulate architectures offer a significant advantage for products that may be used as drug delivery systems in humans. PECs are created by mixing oppositely charged polyions. Their hydrodynamic diameter, surface charge, and polydispersity are highly dependent on concentration, ionic strength, pH, and molecular parameters of the polymers that are used. In particular, the complexation between polyelectrolytes with significantly different molecular weights leads to the formation of water-insoluble aggregates. Several PEC characteristics are favorable for cellular uptake and colloidal stability, including hydrodynamic diameter less than 200 nm, surface charge of >30 mV or <-30 mV, spherical morphology, and polydispersity index (PDI) indicative of a homogeneous distribution. Maintenance of these properties is critical for a successful delivery vehicle. This review focuses on the development and potential applications of PECs as multi-functional, site-specific nanoparticulate drug/gene delivery and imaging devices.

CONJUGATED POLYMERS AND POLYELECTROLYTES IN SOLAR PHOTOCONVERSION, Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schanze, Kirk S

2014-08-05

This DOE-supported program investigated the fundamental properties of conjugated polyelectrolytes, with emphasis placed on studies of excited state energy transport, self-assembly into conjugated polyelectroyte (CPE) based films and colloids, and exciton transport and charge injection in CPE films constructed atop wide bandgap semiconductors. In the most recent grant period we have also extended efforts to examine the properties of low-bandgap donor-acceptor conjugated polyelectrolytes that feature strong visible light absorption and the ability to adsorb to metal-oxide interfaces.

Complexation of ferric oxide particles with pectins of different charge density.

PubMed

Milkova, Viktoria; Kamburova, Kamelia; Petkanchin, Ivana; Radeva, Tsetska

2008-09-02

The effect of polyelectrolyte charge density on the electrical properties and stability of suspensions of oppositely charged oxide particles is followed by means of electro-optics and electrophoresis. Variations in the electro-optical effect and the electrophoretic mobility are examined at conditions where fully ionized pectins of different charge density adsorb onto particles with ionizable surfaces. The charge neutralization point coincides with the maximum of particle aggregation in all suspensions. We find that the concentration of polyelectrolyte, needed to neutralize the particle charge, decreases with increasing charge density of the pectin. The most highly charged pectin presents an exception to this order, which is explained with a reduction of the effective charge density of this pectin due to condensation of counterions. The presence of condensed counterions, remaining bound to the pectin during its adsorption on the particle surface, is proved by investigation of the frequency behavior of the electro-optical effect at charge reversal of the particle surface.

A simple model for electrical charge in globular macromolecules and linear polyelectrolytes in solution

NASA Astrophysics Data System (ADS)

Krishnan, M.

2017-05-01

We present a model for calculating the net and effective electrical charge of globular macromolecules and linear polyelectrolytes such as proteins and DNA, given the concentration of monovalent salt and pH in solution. The calculation is based on a numerical solution of the non-linear Poisson-Boltzmann equation using a finite element discretized continuum approach. The model simultaneously addresses the phenomena of charge regulation and renormalization, both of which underpin the electrostatics of biomolecules in solution. We show that while charge regulation addresses the true electrical charge of a molecule arising from the acid-base equilibria of its ionizable groups, charge renormalization finds relevance in the context of a molecule's interaction with another charged entity. Writing this electrostatic interaction free energy in terms of a local electrical potential, we obtain an "interaction charge" for the molecule which we demonstrate agrees closely with the "effective charge" discussed in charge renormalization and counterion-condensation theories. The predictions of this model agree well with direct high-precision measurements of effective electrical charge of polyelectrolytes such as nucleic acids and disordered proteins in solution, without tunable parameters. Including the effective interior dielectric constant for compactly folded molecules as a tunable parameter, the model captures measurements of effective charge as well as published trends of pKa shifts in globular proteins. Our results suggest a straightforward general framework to model electrostatics in biomolecules in solution. In offering a platform that directly links theory and experiment, these calculations could foster a systematic understanding of the interrelationship between molecular 3D structure and conformation, electrical charge and electrostatic interactions in solution. The model could find particular relevance in situations where molecular crystal structures are not available or rapid, reliable predictions are desired.

Surface adsorption of oppositely charged C14TAB-PAMPS mixtures at the air/water interface and the impact on foam film stability.

PubMed

Fauser, Heiko; von Klitzing, Regine; Campbell, Richard A

2015-01-08

We have studied the oppositely charged polyelectrolyte/surfactant mixture of poly(acrylamidomethylpropanesulfonate) sodium salt (PAMPS) and tetradecyl trimethylammonium bromide (C14TAB) using a combination of neutron reflectivity and ellipsometry measurements. The interfacial composition was determined using three different analysis methods involving the two techniques for the first time. The bulk surfactant concentration was fixed at a modest value while the bulk polyelectrolyte concentration was varied over a wide range. We reveal complex changes in the surface adsorption behavior. Mixtures with low bulk PAMPS concentrations result in the components interacting synergistically in charge neutral layers at the air/water interface. At the bulk composition where PAMPS and C14TAB are mixed in an equimolar charge ratio in the bulk, we observe a dramatic drop in the surfactant surface excess to leave a large excess of polyelectrolyte at the interface, which we infer to have loops in its interfacial structure. Further increase of the bulk PAMPS concentration leads to a more pronounced depletion of material from the surface. Mixtures containing a large excess of PAMPS in the bulk showed enhanced adsorption, which is attributed to the large increase in total ionic strength of the system and screening of the surfactant headgroup charges. The data are compared to our former results on PAMPS/C14TAB mixtures [Kristen et al. J. Phys. Chem. B, 2009, 23, 7986]. A peak in the surface tension is rationalized in terms of the changing surface adsorption and, unlike in more concentrated systems, is unrelated to bulk precipitation. Also, a comparison between the determined interfacial composition with zeta potential and foam film stability data shows that the highest film stability occurs when there is enhanced synergistic adsorption of both components at the interface due to charge screening when the total ionic strength of the system is highest. The additional contribution to the foam stability of the negatively charged polyelectrolyte within the film bulk is also discussed.

Polyphosphates as inorganic polyelectrolytes interacting with oppositely charged ions, polymers and deposited on surfaces: fundamentals and applications.

PubMed

Cini, N; Ball, V

2014-07-01

Polyphosphates are important but neglected polyelectrolytes that play a major role in biology and in surface science for the stabilization of colloids against flocculation and for the preservation of food. They are also known as "Calgon" ® and intensively used as additives in washing powders. This review aims to review recent developments in which linear polyphosphates are used for the design of new functional coatings using sol-gel processes and layer-by-layer deposition methods. All these methods rely on the high charge density of polyphosphates as inorganic polyelectrolytes, therefore the structure and properties of these molecules are also reviewed. New perspectives will also been given for the design of stimuli responsive coatings at the tiny frontier between biology and materials science. Copyright © 2014 Elsevier B.V. All rights reserved.

Finite-size polyelectrolyte bundles at thermodynamic equilibrium

NASA Astrophysics Data System (ADS)

Sayar, M.; Holm, C.

2007-01-01

We present the results of extensive computer simulations performed on solutions of monodisperse charged rod-like polyelectrolytes in the presence of trivalent counterions. To overcome energy barriers we used a combination of parallel tempering and hybrid Monte Carlo techniques. Our results show that for small values of the electrostatic interaction the solution mostly consists of dispersed single rods. The potential of mean force between the polyelectrolyte monomers yields an attractive interaction at short distances. For a range of larger values of the Bjerrum length, we find finite-size polyelectrolyte bundles at thermodynamic equilibrium. Further increase of the Bjerrum length eventually leads to phase separation and precipitation. We discuss the origin of the observed thermodynamic stability of the finite-size aggregates.

Alcohol--Induced Polyelectrolyte-Surfactant Complex Coacervate Systems: Characterization and Applications in Enzyme and Protein Extraction

NASA Astrophysics Data System (ADS)

Nejati Moshtaghin, Mahboubeh

The focus of this thesis is to achieve a better understanding of the newly discovered surfactant-polyelectrolyte complex coacervate (SPCC) systems induced by fluoroalcohol/acid as well as short chain aliphatic alcohol; and to elucidate their applications in extraction and enrichment of proteins and enzyme. We have discovered that fluoroalcohols and --acids induce complex coacervation and phase separation in the aqueous mixtures of oppositely charged anionic polyelectrolytes; specifically, sodium salts of polyacrylic acid and polymethacrylic acid and cationic surfactant (cetyltrimethylammonium bromide, CTAB) over a broad range of concentrations of mole fractions of the oppositely charged amphiphiles. Accordingly, these new classes of coacervators will significantly broaden the scope and facilitate engineering of new coacervate phases. Toward these goals, we have inspected the formation of surfactant-polyelectrolyte complex coacervates in the presence of fluoroalcohols namely hexafluoroisopropanol (HFIP) and Trifluoroethanol (TFE). Furthermore, the extent of coacervation as a function of concentrations the system components, and charge ratios of the oppositely charged amphiphiles has been investigated. Polyelectrolytes are considered to be milder reagents, as compared to surfactants, regarding proteins denaturation. This highlights the importance of a detailed investigation of the efficiency of our coacervate systems for extraction and preconcentration of proteins and enzymes, especially, when the biological activity of the extracted proteins needs to be maintained based on the objectives mentioned above, the results of the investigations have been organized in four chapters. In Chapter II, the phase behavior of the FA-SPCC will be investigated. The objective is to examine the phase behavior and phase properties with respect to the extent of coacervation in different solution conditions. In particular, the effects of different solution variables such as concentration of FA, oppositely charged amphiphiles (surfactant-polyelectrolyte), and the charge ratio of the surfactant-polyelectrolyte on the extent of coacervation have been investigated. Furthermore, the chemical composition of each phase formed in the coacervate system was determined as a function of HFIP percentage. Phase diagrams of HFIP-PMA-CTAB and 2-propanol-PMA-CTAB were studied. The phase separation occurs over a wide range of polyelectrolyte, surfactant and alcohol concentration. In addition, a study of the dependence of coacervate volume on phase composition in different system (as defined by concentrations and mole charge ratio of amphihiles and alcohols) provided useful insight about possible underlying interactions and mechanisms. It has been concluded that neutralization favors coacervation in both systems. However, according to the compositional analysis of both HFIP and 2-propanol SPCC system, it seems that coacervation mechanisms are different. In Chapter III the properties of 2-propanol--SPCC, with analogous surfactant (CTAB) and polyelectrolyte (PMA) used in Chapter II, will be investigated. In particular, we are interested in examining the difference between the phase separation characteristics of the coacervates induced by 2-propanol and HFIP as coacervator. For this purpose, the phase behavior and the chemical composition of the phases will be analyzed as a function of 2-propanol and constituents concentrations. Chapter IV contains results of our investigations on the activity of a model enzyme (Trypsin) in 2-propanol- and FA-induced SPCC system. These investigations will facilitate understanding whether the aliphatic alcohol, AA- and FA-induced SPCC system denature the model enzymes. Such investigations also help in evaluation of the applicability of the coacervate systems developed in this work in proteomics where the proteolytic activity of enzymes is used for protein digestion. Finally, in Chapter V, the efficiency of the coacervate system (2-propanol-induced-PMA-CTAB) for extraction of cytochrome c, as a model protein, will be investigated.

Resistance of poly(ethylene oxide)-silane monolayers to the growth of polyelectrolyte multilayers.

PubMed

Buron, Cédric C; Callegari, Vincent; Nysten, Bernard; Jonas, Alain M

2007-09-11

The ability of poly(ethylene oxide)-silane (PEO-silane) monolayers grafted onto silicon surfaces to resist the growth of polyelectrolyte multilayers under various pH conditions is assessed for different pairs of polyelectrolytes of varying molar mass. For acidic conditions (pH 3), the PEO-silane monolayers exhibit good polyelectrolyte repellency provided the polyelectrolytes bear no moieties that are able to form hydrogen bonds with the ether groups of the PEO chains. At basic pH, PEO-silane monolayers undergo substantial hydrolysis leading to the formation of negatively charged defects in the monolayers, which then play the role of adsorption sites for the polycation. Once the polycation is adsorbed, multilayer growth ensues. Because this is defect-driven growth, the multilayer is not continuous and is made of blobs or an open network of adsorbed strands. For such conditions, the molar mass of the polyelectrolyte plays a key role, with polyelectrolyte chains of larger molar mass adsorbing on a larger number of defects, resulting in stronger anchoring of the polyelectrolyte complex on the surfaces and faster subsequent growth of the multilayer. For polyelectrolytes of sufficiently low molar mass at pH 9, the growth of the multilayer can nevertheless be prevented for as much as five cycles of deposition.

Ion transferring in polyelectrolyte networks in electric fields

NASA Astrophysics Data System (ADS)

Li, Honghao; Erbas, Aykut; Zwanikken, Jos; Olvera de La Cruz, Monica

Ion-conducting polyelectrolyte gels have drawn the attention of many researchers in the last few decades as they have wide applications not only in lithium batteries but also as stretchable, transparent ionic conductor or ionic cables devices. However, ion dynamics in polyelectrolyte gels has been much less studied analytically or computationally due to the complicated interplay of long-range electrostatic and short-range interactions. Here we propose a coarse-grained non-equilibrium molecular dynamics simulation to study the ion dynamics in polyelectrolyte gels under external electric fields. We found a nonlinear response region where the molar conductivity of polyelectrolyte gels increases with external fields. We propose counterion redistribution under electric fields as the driving mechanism. We also found the ionic conductivity to be modulated by changing polylelectrolyte network topology such as the chain length. Our discovery reveals the essential difference of ion dynamics between electrolytes and polyelectrolyte gels. These results will expand our understanding in charged polymeric systems and help in designing ion-conducting devices with higher conductivity.

Potential of mean force between like-charged nanoparticles: Many-body effect

NASA Astrophysics Data System (ADS)

Zhang, Xi; Zhang, Jin-Si; Shi, Ya-Zhou; Zhu, Xiao-Long; Tan, Zhi-Jie

2016-03-01

Ion-mediated interaction is important for the properties of polyelectrolytes such as colloids and nucleic acids. The effective pair interactions between two polyelectrolytes have been investigated extensively, but the many-body effect for multiple polyelectrolytes still remains elusive. In this work, the many-body effect in potential of mean force (PMF) between like-charged nanoparticles in various salt solutions has been comprehensively examined by Monte Carlo simulation and the nonlinear Poisson-Boltzmann theory. Our calculations show that, at high 1:1 salt, the PMF is weakly repulsive and appears additive, while at low 1:1 salt, the additive assumption overestimates the repulsive many-body PMF. At low 2:2 salt, the pair PMF appears weakly repulsive while the many-body PMF can become attractive. In contrast, at high 2:2 salt, the pair PMF is apparently attractive while the many-body effect can cause a weaker attractive PMF than that from the additive assumption. Our microscopic analyses suggest that the elusive many-body effect is attributed to ion-binding which is sensitive to ion concentration, ion valence, number of nanoparticles and charges on nanoparticles.

Efficient Energy Conversion by Grafting Nanochannels with End-charged Stimuli-responsive Polyelectrolyte Brush

NASA Astrophysics Data System (ADS)

Chen, Guang; Das, Siddhartha

2017-11-01

Polyelectrolyte (PE) brushes have aroused increasing attention in applications in energy conversion and chemical sensing due to the environmentally-responsive and designable nature. PE brushes are charged polymer chains densely grafted on solid-liquid interfaces. By designing copolymeric systems, one can localize the ionizable sites at the brush tip in order to get end-charged PE brushes. Such brushes demonstrate anomalous shrinking/swelling behaviors with tunable environmental parameters such as pH and salt concentration. In this study, we probe the conformation and electrostatics of such PE brush systems with various size, grafting density and charge distribution, and exploit the electrochemomechanical energy conversion capabilities of nanochannels grafted with such PE brush systems. Our results indicate that the presence of the end-charged PE brush layer can massively enhance the streaming potential mediated energy conversion efficiency, and the improvement is more significant in strongly ionic solution.

Synthesis and Properties of a Precision Sulfonated Trimethylene-Styrene Polyelectrolyte

NASA Astrophysics Data System (ADS)

Kennemur, Justin; Neary, William; Bohlmann, Michele; Kendrick, Aaron

We recently reported successful ring-opening metathesis polymerization of 4-phenylcyclopentene to afford a precision ethylene-styrene type copolymer with a phenyl branch at exactly every fifth carbon along the backbone following mild hydrogenation of the backbone olefins. (http://dx.doi.org/10.1002/marc.201600121) Compared to polystyrene, this material shows a markedly reduced glass transition temperature (Tg 17 °C) and remains amorphous. We have now extended the function of this polymer via sulfonation of the phenyl branches to produce a precision polyelectrolyte with an ionic charge spacing at every fifth carbon along the chain. The reduced yet precise charge density coupled with the low Tg of the native material translates into a variety of properties that are unique to this system and potentially useful as an addition to the limited set of available polyelectrolyte materials. Synthetic aspects in addition to thermal and mechanical properties will be discussed. Graduate Student.

Ferroelectric polarization induces electric double layer bistability in electrolyte-gated field-effect transistors.

PubMed

Fabiano, Simone; Crispin, Xavier; Berggren, Magnus

2014-01-08

The dense surface charges expressed by a ferroelectric polymeric thin film induce ion displacement within a polyelectrolyte layer and vice versa. This is because the density of dipoles along the surface of the ferroelectric thin film and its polarization switching time matches that of the (Helmholtz) electric double layers formed at the ferroelectric/polyelectrolyte and polyelectrolyte/semiconductor interfaces. This combination of materials allows for introducing hysteresis effects in the capacitance of an electric double layer capacitor. The latter is advantageously used to control the charge accumulation in the semiconductor channel of an organic field-effect transistor. The resulting memory transistors can be written at a gate voltage of around 7 V and read out at a drain voltage as low as 50 mV. The technological implication of this large difference between write and read-out voltages lies in the non-destructive reading of this ferroelectric memory.

Regimes of electrostatic collapse of a highly charged polyelectrolyte in a poor solvent.

PubMed

Tom, Anvy Moly; Vemparala, Satyavani; Rajesh, R; Brilliantov, Nikolai V

2017-03-01

We perform extensive molecular dynamics simulations of a highly charged, collapsed, flexible polyelectrolyte chain in a poor solvent for the case when the electrostatic interactions, characterized by the reduced Bjerrum length l B , are strong. We find the existence of several sub-regimes in the dependence of the gyration radius of the chain R g on l B characterized by R g ∼ l. In contrast to a good solvent, the exponent γ for a poor solvent crucially depends on the size and valency of the counterions. To explain the different sub-regimes, we generalize the existing counterion fluctuation theory by including a more complete account of all possible volume interactions in the free energy of the polyelectrolyte chain. We also show that the presence of condensed counterions modifies the effective attraction among the chain monomers and modulates the sign of the second virial coefficient under poor solvent conditions.

Coarse-grained modeling of proline rich protein 1 (PRP-1) in bulk solution and adsorbed to a negatively charged surface.

PubMed

Skepö, Marie; Linse, Per; Arnebrant, Thomas

2006-06-22

Structural properties of the acidic proline rich protein PRP-1 of salivary origin in bulk solution and adsorbed onto a negatively charged surface have been studied by Monte Carlo simulations. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. In addition to PRP-1, some mutants were considered to assess the role of the interactions in the systems. Contrary to polyelectrolytes, the protein has a compact structure in salt-free bulk solutions, whereas at high salt concentration the protein becomes more extended. The protein adsorbs to a negatively charged surface, although its net charge is negative. The adsorbed protein displays an extended structure, which becomes more compact upon addition of salt. Hence, the conformational response upon salt addition in the adsorbed state is the opposite as compared to that in bulk solution. The conformational behavior of PRP-1 in bulk solution and at charged surfaces as well as its propensity to adsorb to surfaces with the same net charge are rationalized by the block polyampholytic character of the protein. The presence of a triad of positively charged amino acids in the C-terminal was found to be important for the adsorption of the protein.

Folding Behaviors of Protein (Lysozyme) Confined in Polyelectrolyte Complex Micelle.

PubMed

Wu, Fu-Gen; Jiang, Yao-Wen; Chen, Zhan; Yu, Zhi-Wu

2016-04-19

The folding/unfolding behavior of proteins (enzymes) in confined space is important for their properties and functions, but such a behavior remains largely unexplored. In this article, we reported our finding that lysozyme and a double hydrophilic block copolymer, methoxypoly(ethylene glycol)5K-block-poly(l-aspartic acid sodium salt)10 (mPEG(5K)-b-PLD10), can form a polyelectrolyte complex micelle with a particle size of ∼30 nm, as verified by dynamic light scattering and transmission electron microscopy. The unfolding and refolding behaviors of lysozyme molecules in the presence of the copolymer were studied by microcalorimetry and circular dichroism spectroscopy. Upon complex formation with mPEG(5K)-b-PLD10, lysozyme changed from its initial native state to a new partially unfolded state. Compared with its native state, this copolymer-complexed new folding state of lysozyme has different secondary and tertiary structures, a decreased thermostability, and significantly altered unfolding/refolding behaviors. It was found that the native lysozyme exhibited reversible unfolding and refolding upon heating and subsequent cooling, while lysozyme in the new folding state (complexed with the oppositely charged PLD segments of the polymer) could unfold upon heating but could not refold upon subsequent cooling. By employing the heating-cooling-reheating procedure, the prevention of complex formation between lysozyme and polymer due to the salt screening effect was observed, and the resulting uncomplexed lysozyme regained its proper unfolding and refolding abilities upon heating and subsequent cooling. Besides, we also pointed out the important role the length of the PLD segment played during the formation of micelles and the monodispersity of the formed micelles. Furthermore, the lysozyme-mPEG(5K)-b-PLD10 mixtures prepared in this work were all transparent, without the formation of large aggregates or precipitates in solution as frequently observed in other protein-polyelectrolyte systems. Hence, the present protein-PEGylated poly(amino acid) mixture provides an ideal water-soluble model system to study the important role of electrostatic interaction in the complexation between proteins and polymers, leading to important new knowledge on the protein-polymer interactions. Moreover, the polyelectrolyte complex micelle formed between protein and PEGylated polymer may provide a good drug delivery vehicle for therapeutic proteins.

Properties of POPC/POPE supported lipid bilayers modified with hydrophobic quantum dots on polyelectrolyte cushions.

PubMed

Kolasinska-Sojka, Marta; Wlodek, Magdalena; Szuwarzynski, Michal; Kereiche, Sami; Kovacik, Lubomir; Warszynski, Piotr

2017-10-01

The formation and properties of supported lipid bilayers (SLB) containing hydrophobic nanoparticles (NP) was studied in relation to underlying cushion obtained from selected polyelectrolyte multilayers. Lipid vesicles were formed from zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and negatively charged 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) in phosphate buffer (PBS). As hydrophobic nanoparticles - quantum dots (QD) with size of 3.8nm (emission wavelength of 420nm) were used. Polyelectrolyte multilayers (PEM) were constructed by the sequential, i.e., layer-by-layer (LbL) adsorption of alternately charged polyelectrolytes from their solutions. Liposomes and Liposome-QDs complexes were studied with Transmission Cryo-Electron Microscopy (Cryo-TEM) to verify the quality of vesicles and the position of QD within lipid bilayer. Deposition of liposomes and liposomes with quantum dots on polyelectrolyte films was studied in situ using quartz crystal microbalance with dissipation (QCM-D) technique. The fluorescence emission spectra were analyzed for both: suspension of liposomes with nanoparticles and for supported lipid bilayers containing QD on PEM. It was demonstrated that quantum dots are located in the hydrophobic part of lipid bilayer. Moreover, we proved that such QD-modified liposomes formed supported lipid bilayers and their final structure depended on the type of underlying cushion. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of nanodimensional polyethylenimine layer on surface potential barriers of hybrid structures based on silicon single crystal

NASA Astrophysics Data System (ADS)

Malyar, Ivan V.; Gorin, Dmitry A.; Stetsyura, Svetlana V.

2013-01-01

In this report we present the analysis of I-V curves for MIS-structures like silicon substrate / nanodimensional polyelectrolyte layer / metal probe (contact) which is promising for biosensors, microfluidic chips, different devices of molecular electronics, such as OLEDs, solar cells, where polyelectrolyte layers can be used to modify semiconductor surface. The research is directed to investigate the contact phenomena which influence the resulting signal of devices mentioned above. The comparison of I-V characteristics of such structures measured by scanning tunnel microscopy (contactless technique) and using contact areas deposited by thermal evaporation onto the organic layer (the contact one) was carried out. The photoassisted I-V measurements and complex analysis based on Simmons and Schottky models allow one to extract the potential barriers and to observe the changes of charge transport in MIS-structures under illumination and after polyelectrolyte adsorption. The direct correlation between the thickness of the deposited polyelectrolyte layer and both equilibrium tunnel barrier and Schottky barrier height was observed for hybrid structures with polyethylenimine. The possibility of control over the I-V curves of hybrid structure and the height of the potential barriers (for different charge transports) by illumination was confirmed. Based on experimental data and complex analysis the band diagrams were plotted which illustrate the changes of potential barriers for MIS-structures due to the polyelectrolyte adsorption and under the illumination.

Polyelectrolyte Complex Optimization for Macrophage Delivery of Redox Enzyme Nanoparticles

PubMed Central

Zhao, Yuling; Haney, Matthew J.; Klyachko, Natalia L.; Li, Shu; Booth, Stephanie L.; Higginbotham, Sheila M.; Jones, Jocelyn; Zimmerman, Matthew C.; Mosley, R. Lee; Kabanov, Alexander V.; Gendelman, Howard E.; Batrakova, Elena V.

2011-01-01

Background We posit that cell-mediated drug delivery can improve transport of therapeutic enzymes to the brain and decrease inflammation and neurodegeneration induced during Parkinson’s disease. Our prior work demonstrated that macrophages loaded with nanoformulated catalase (“nanozyme”) protect the nigrostriatum in a murine model of Parkinson’s disease. Packaging of catalase into block ionomer complex with a synthetic polyelectrolyte block copolymers protects the enzyme degradation in macrophages. Methods We examined relationships between the composition and structure of block ionomer complexes, their physicochemical characteristics, and loadings, release rates, and catalase activity in bone marrow-derived macrophages. Results Formation of block-ionomer complexes resulted in improved aggregation stability. Block ionomer complexes with ε-polylisine, and poly-L-glutamic acid -poly(ethylene glycol) demonstrated the least cytotoxicity and high loading and release rates, however, did not efficiently protect catalase inside macrophages. Conclusion nanozymes with polyethyleneimine- and poly(L-lysine)10-poly(ethylene glycol) provided the best protection of enzymatic activity for cell-mediated drug delivery. PMID:21182416

Ultrasensitive detection of nitroexplosive - picric acid via a conjugated polyelectrolyte in aqueous media and solid support.

PubMed

Hussain, Sameer; Malik, Akhtar Hussain; Afroz, Mohammad Adil; Iyer, Parameswar Krishnan

2015-04-28

Picric acid (PA) detection at parts per trillion (ppt) levels is achieved by a conjugated polyelectrolyte (PMI) in 100% aqueous media and on a solid platform using paper strips and chitosan (CS) films. The unprecedented selectivity is accomplished via combination of ground state charge transfer and resonance energy transfer (RET) facilitated by favorable electrostatic interactions.

Interaction of Charged Patchy Protein Models with Like-Charged Polyelectrolyte Brushes.

PubMed

Yigit, Cemil; Kanduč, Matej; Ballauff, Matthias; Dzubiella, Joachim

2017-01-10

We study the adsorption of charged patchy particle models (CPPMs) on a thin film of a like-charged and dense polyelectrolyte (PE) brush (of 50 monomers per chain) by means of implicit-solvent, explicit-salt Langevin dynamics computer simulations. Our previously introduced set of CPPMs embraces well-defined one- and two-patched spherical globules, each of the same net charge and (nanometer) size, with mono- and multipole moments comparable to those of small globular proteins. We focus on electrostatic effects on the adsorption far away from the isoelectric point of typical proteins, i.e., where charge regulation plays no role. Despite the same net charge of the brush and globule, we observe large binding affinities up to tens of the thermal energy, k B T, which are enhanced by decreasing salt concentration and increasing charge of the patch(es). Our analysis of the distance-resolved potentials of mean force together with a phenomenological description of all leading interaction contributions shows that the attraction is strongest at the brush surface, driven by multipolar, Born (self-energy), and counterion-release contributions, dominating locally over the monopolar and steric repulsions.

[Interaction of protein with charged colloidal particles].

PubMed

Durdenko, E V; Kuznetsova, S M; Basova, L V; Tikhonenko, S A; Saburova, E A

2011-01-01

The functional state of three proteins of different molecular weight (urease, lactate dehydrogenase, and hemoglobin) in the presence of the linear polyelectrolytes poly(allylamine hydrochloride) (PAA) and sodium poly(styrenesulfonate) (PSS) in the dissolved state and of the same polyelectrolytes bound to the surface of microspheres has been investigated. Microspheres were prepared by consecutive absorption of oppositely charged polyelectrolytes so that the outer layer of the shell was PAA for the acidic protein urease, and PSS for the alkaline proteins LDH and hemoglobin. It was shown that the dissolved polyelectrolyte completely inactivates all three proteins within one minute with a slight difference in the time constant. (By Hb inactivation are conventionally meant changes in the heme environment observed from the spectrum in the Soret band.) In the presence of microspheres, the proteins were adsorbed on their surface; in this case, more than 95% of the activity was retained within two hours. The proportion of the protein adsorbed on microspheres accounted for about 98% for urease, 72% for Hb, and 35% for LDH, as determined from the tryptophan fluorescence data. The interaction of hemoglobin with another type of charged colloidal particles, phospholipid vesicles, leads to the destruction of the tertiary structure of the protein, which made itself evident in the optical absorption spectra in the Soret band, as well as the spectra of tryptophan fluorescence and circular dichroism. In this case, according to circular dichroism, the percentage of alpha-helical structure of Hb was maintained. The differences in the physical and chemical mechanisms of interaction of proteins with these two types of charged colloidal particles that leads to differences in the degree of denaturing effects are discussed.

Modeling the formation of ordered nano-assemblies comprised by dendrimers and linear polyelectrolytes: The role of Coulombic interactions

NASA Astrophysics Data System (ADS)

Eleftheriou, E.; Karatasos, K.

2012-10-01

Models of mixtures of peripherally charged dendrimers with oppositely charged linear polyelectrolytes in the presence of explicit solvent are studied by means of molecular dynamics simulations. Under the influence of varying strength of electrostatic interactions, these systems appear to form dynamically arrested film-like interconnected structures in the polymer-rich phase. Acting like a pseudo-thermodynamic inverse temperature, the increase of the strength of the Coulombic interactions drive the polymeric constituents of the mixture to a gradual dynamic freezing-in. The timescale of the average density fluctuations of the formed complexes initially increases in the weak electrostatic regime reaching a finite limit as the strength of electrostatic interactions grow. Although the models are overall electrically neutral, during this process the dendrimer/linear complexes develop a polar character with an excess charge mainly close to the periphery of the dendrimers. The morphological characteristics of the resulted pattern are found to depend on the size of the polymer chains on account of the distinct conformational features assumed by the complexed linear polyelectrolytes of different length. In addition, the length of the polymer chain appears to affect the dynamics of the counterions, thus affecting the ionic transport properties of the system. It appears, therefore, that the strength of electrostatic interactions together with the length of the linear polyelectrolytes are parameters to which these systems are particularly responsive, offering thus the possibility for a better control of the resulted structure and the electric properties of these soft-colloidal systems.

Solvent-Vapor-Mitigation of Electrostatics in 3D Cyclopropenium Diblock Copolyelectrolyte Network

NASA Astrophysics Data System (ADS)

Russell, Sebastian; Kumar, Sanat; Campos, Luis

Photolithography is progressively becoming an obsolete manufacturing technique in the microelectronic industry as block copolymer (BCP) nanoassembles approach sub 10-nm features sizes. Thermodynamically, the morphology and limiting feature size, for BCP, are determined by the relative volume fraction and magnitude of the incompatibility (χN) between each block. Therefore, to achieve smaller dimensions, it is imperative to devise copolymer systems that are strongly segregating (χN >>10) by utilizing high monomer incompatibility, large χ. For synthetic cylinder forming BCPs, achieving sub-10 nm features with a high degree of lateral ordering still remains a challenge. Covalently bound ions could potentially be a route towards enhancing the segmental incompatibility and this presentation will focus on the self-assembly of post-polymerization functionalized cyclopropenium-ion diblock copolyelectrolytes (DBCPE) through solvent vapor annealing. By varying the BCPE's total degree of polymerization and charge fraction we have mapped the kinetic phase-space. This control over morphology has opened the door to sub-10nm features with tunable densities by varying the length of the neutral and polyelectrolyte block, respectively. Chemical Engineering Department.

Computer simulations of dendrimer-polyelectrolyte complexes.

PubMed

Pandav, Gunja; Ganesan, Venkat

2014-08-28

We carry out a systematic analysis of static properties of the clusters formed by complexation between charged dendrimers and linear polyelectrolyte (LPE) chains in a dilute solution under good solvent conditions. We use single chain in mean-field simulations and analyze the structure of the clusters through radial distribution functions of the dendrimer, cluster size, and charge distributions. The effects of LPE length, charge ratio between LPE and dendrimer, the influence of salt concentration, and the dendrimer generation number are examined. Systems with short LPEs showed a reduced propensity for aggregation with dendrimers, leading to formation of smaller clusters. In contrast, larger dendrimers and longer LPEs lead to larger clusters with significant bridging. Increasing salt concentration was seen to reduce aggregation between dendrimers as a result of screening of electrostatic interactions. Generally, maximum complexation was observed in systems with an equal amount of net dendrimer and LPE charges, whereas either excess LPE or dendrimer concentrations resulted in reduced clustering between dendrimers.

Simulations of stretching a flexible polyelectrolyte with varying charge separation

DOE PAGES

Stevens, Mark J.; Saleh, Omar A.

2016-07-22

We calculated the force-extension curves for a flexible polyelectrolyte chain with varying charge separations by performing Monte Carlo simulations of a 5000 bead chain using a screened Coulomb interaction. At all charge separations, the force-extension curves exhibit a Pincus-like scaling regime at intermediate forces and a logarithmic regime at large forces. As the charge separation increases, the Pincus regime shifts to a larger range of forces and the logarithmic regime starts are larger forces. We also found that force-extension curve for the corresponding neutral chain has a logarithmic regime. Decreasing the diameter of bead in the neutral chain simulations removedmore » the logarithmic regime, and the force-extension curve tends to the freely jointed chain limit. In conclusion, this result shows that only excluded volume is required for the high force logarithmic regime to occur.« less

Interactions between ionic liquid surfactant [C12mim]Br and DNA in dilute brine.

PubMed

He, Yunfei; Shang, Yazhuo; Liu, Zhenhai; Shao, Shuang; Liu, Honglai; Hu, Ying

2013-01-01

Interactions between ionic liquid surfactant [C(12)mim]Br and DNA in dilute brine were investigated in terms of various experimental methods and molecular dynamics (MD) simulation. It was shown that the aggregation of [C(12)mim]Br on DNA chains is motivated not only by electrostatic attractions between DNA phosphate groups and [C(12)mim]Br headgroups but also by hydrophobic interactions among [C(12)mim]Br alkyl chains. Isothermal titration calorimetry analysis indicated that the [C(12)mim]Br aggregation in the presence and absence of DNA are both thermodynamically favored driven by enthalpy and entropy. DNA undergoes size transition and conformational change induced by [C(12)mim]Br, and the charges of DNA are neutralized by the added [C(12)mim]Br. Various microstructures were observed such as DNA with loose coil conformation in nature state, necklace-like structures, and compact spherical aggregates. MD simulation showed that the polyelectrolyte collapses upon the addition of oppositely charged surfactants and the aggregation of surfactants around the polyelectrolyte was reaffirmed. The simulation predicted the gradual neutralization of the negatively charged polyelectrolyte by the surfactant, consistent with the experimental results. Copyright © 2012 Elsevier B.V. All rights reserved.

Strong and weak adsorptions of polyelectrolyte chains onto oppositely charged spheres

NASA Astrophysics Data System (ADS)

Cherstvy, A. G.; Winkler, R. G.

2006-08-01

We investigate the complexation of long thin polyelectrolyte (PE) chains with oppositely charged spheres. In the limit of strong adsorption, when strongly charged PE chains adapt a definite wrapped conformation on the sphere surface, we analytically solve the linear Poisson-Boltzmann equation and calculate the electrostatic potential and the energy of the complex. We discuss some biological applications of the obtained results. For weak adsorption, when a flexible weakly charged PE chain is localized next to the sphere in solution, we solve the Edwards equation for PE conformations in the Hulthén potential, which is used as an approximation for the screened Debye-Hückel potential of the sphere. We predict the critical conditions for PE adsorption. We find that the critical sphere charge density exhibits a distinctively different dependence on the Debye screening length than for PE adsorption onto a flat surface. We compare our findings with experimental measurements on complexation of various PEs with oppositely charged colloidal particles. We also present some numerical results of the coupled Poisson-Boltzmann and self-consistent field equation for PE adsorption in an assembly of oppositely charged spheres.

Formulation and stabilization of nano-/microdispersion systems using naturally occurring edible polyelectrolytes by electrostatic deposition and complexation.

PubMed

Kuroiwa, Takashi; Kobayashi, Isao; Chuah, Ai Mey; Nakajima, Mitsutoshi; Ichikawa, Sosaku

2015-12-01

This review paper presents an overview of the formulation and functionalization of nano-/microdispersion systems composed of edible materials. We first summarized general aspects on the stability of colloidal systems and the roles of natural polyelectrolytes such as proteins and ionic polysaccharides for the formation and stabilization of colloidal systems. Then we introduced our research topics on (1) stabilization of emulsions by the electrostatic deposition using natural polyelectrolytes and (2) formulation of stable nanodispersion systems by complexation of natural polyelectrolytes. In both cases, the preparation procedures were relatively simple, without high energy input or harmful chemical addition. The properties of the nano-/microdispersion systems, such as particle size, surface charge and dispersion stability were significantly affected by the concerned materials and preparation conditions, including the type and concentration of used natural polyelectrolytes. These dispersion systems would be useful for developing novel foods having high functionality and good stability. Copyright © 2015 Elsevier B.V. All rights reserved.

Flocculation of Clay Colloids Induced by Model Polyelectrolytes: Effects of Relative Charge Density and Size.

PubMed

Sakhawoth, Yasine; Michot, Laurent J; Levitz, Pierre; Malikova, Natalie

2017-10-06

Flocculation and its tuning are of utmost importance in the optimization of several industrial protocols in areas such as purification of waste water and civil engineering. Herein, we studied the polyelectrolyte-induced flocculation of clay colloids on a model system consisting of purified clay colloids of well-defined size fractions and ionene polyelectrolytes presenting regular and tunable chain charge density. To characterize ionene-induced clay flocculation, we turned to the combination of light absorbance (turbidity) and ζ-potential measurements, as well as adsorption isotherms. Our model system allowed us to identify the exact ratio of positive and negative charges in clay-ionene mixtures, the (c+/c-) ratio. For all samples studied, the onset of efficient flocculation occurred consistently at c+/c- ratios significantly below 1, which indicated the formation of highly ionene-deficient aggregates. At the same time, the ζ-potential measurements indicated an apparent zero charge on such aggregates. Thus, the ζ-potential values could not provide the stoichiometry inside the clay-ionene aggregates. The early onset of flocculation in clay-ionene mixtures is reminiscent of the behavior of multivalent salts and contrasts that of monovalent salts, for which a large excess amount of ions is necessary to achieve flocculation. Clear differences in the flocculation behavior are visible as a function of the ionene charge density, which governs the conformation of the ionene chains on the clay surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium polyelectrolyte bundles with different multivalent counterion concentrations

NASA Astrophysics Data System (ADS)

Sayar, Mehmet; Holm, Christian

2010-09-01

We present the results of molecular-dynamics simulations on the salt concentration dependence of the formation of polyelectrolyte bundles in thermodynamic equilibrium. Extending our results on salt-free systems we investigate here deficiency or excess of trivalent counterions in solution. Our results reveal that the trivalent counterion concentration significantly alters the bundle size and size distribution. The onset of bundle formation takes place at earlier Bjerrum length values with increasing trivalent counterion concentration. For the cases of 80%, 95%, and 100% charge compensation via trivalent counterions, the net charge of the bundles decreases with increasing size. We suggest that competition among two different mechanisms, counterion condensation and merger of bundles, leads to a nonmonotonic change in line-charge density with increasing Bjerrum length. The investigated case of having an abundance of trivalent counterions by 200% prohibits such a behavior. In this case, we find that the difference in effective line-charge density of different size bundles diminishes. In fact, the system displays an isoelectric point, where all bundles become charge neutral.

Polyelectrolyte Properties in Mono and Multi-Valent Ionic Media: Brushes and Complex Coacervates

NASA Astrophysics Data System (ADS)

Farina, Robert M.

Materials composed of polyelectrolytes have unique and interesting physical properties resulting primarily from their charged monomer segments. Polyelectrolytes, which exist in many different biological and industrial forms, have also been shown to be highly responsive to external environmental changes. Here, two specific polyelectrolyte systems, brushes and complex coacervates, are discussed in regards to how their properties can be tailored by adjusting the surrounding ionic environment with mono and multi-valent ions. End-tethered polyelectrolyte brushes, which constitute an interesting and substantial portion of polyelectrolyte applications, are well known for their ability to provide excellent lubrication and low friction when coated onto surfaces (e.g. articular cartilage and medical devices), as well as for their ability to stabilize colloidal particles in solution (e.g. paint and cosmetic materials). These properties have been extensively studied with brushes in pure mono-valent ionic media. However, polyelectrolyte brush interactions with multi-valent ions in solution are much less understood, although highly relevant considering mono and multi-valent counterions are present in most applications. Even at very low concentrations of multi-valent ions in solution, dramatic polyelectrolyte brush physical property changes can occur, resulting in collapsed chains which also adhere to one another via multi-valent bridging. Here, the strong polyelectrolyte poly(sodium styrene sulfonate) was studied using the Surface Forces Apparatus (SFA) and electrochemistry in order to investigate brush height and intermolecular interactions between two brushes as a function of multi-valent counterion population inside a brush. Complex coacervates are formed when polyanions and polycations are mixed together in proper conditions of an aqueous solution. This mixing results in a phase separation of a polymer-rich, coacervate phase composed of a chain network held together via electrostatic interactions. Complex coacervates are highly regarded for their extremely low interfacial energy resulting in an ability to spread and adhere to surfaces under water, utilized by marine organisms (e.g. mussels and tubeworms), as well as many encapsulation applications (e.g. pigment encapsulation for carbon-less paper and electronic paper displays). Here, the interfacial energy of coacervates composed of oppositely charged polypeptides, poly(L-lysine) and poly(L-glutamic acid), was investigated using the SFA in regards to changes in bulk mono-valent salt concentrations.

Modeling pH-Responsive Adsorption of Polyelectrolytes at Oil-Water Interfaces

NASA Astrophysics Data System (ADS)

Qin, Shiyi; Yong, Xin

We use dissipative particle dynamics (DPD) to discover the interfacial adsorption of pH-responsive polyelectrolytes in oil-water binary systems under different pH values. The electrostatic interactions between charged beads and the dielectric discontinuity across the interface are modeled by exploiting a modified Particle-Particle-Particle-Mesh (PPPM) method, which uses an iterative method to solve the Poisson equation on a uniform grid. We first model the adsorption behavior of a single linear polyelectrolyte from the aqueous phase. The Henderson-Hasselbalch equation describes the relation between pH and the degree of ionization of the modeled polyelectrolytes. Through changing the degree of ionization, we explore the influence of pH on the adsorption behavior and show that the electrostatic interactions significantly modulate the adsorption. Time evolutions of the position and conformation of the polyelectrolytes and the variation in the oil-water surface tension will be measured to characterize the adsorption behavior. Furthermore, we model the pH-dependent adsorption behavior of polyelectrolytes with more complicated structures, namely, branched polyelectrolytes with hydrophobic backbones and hydrophilic side chains. We also find that the addition of salts in the medium and the lengths of the backbone and ionized side chain affect the adsorption. This research supported by the American Chemical Society Petroleum Research Fund (Award 56884-DNI9).

Differences between tethered polyelectrolyte chains adsorbed onto bare mica and hydrophobically modified mica, comparison with theory.

NASA Astrophysics Data System (ADS)

Balastre, Marc; Tamashiro, Mario N.; Hernandez, Ernesto; Pincus, Philip; Tirrell, Matthew

2001-03-01

End-grafted polymers generated from the adsorption of asymmetric diblock copolymers on solid surface play an important role in many areas of science and technology. While the small insoluble block acts as an anchor, the charged soluble block confers useful properties to the surface. This study looks at tethered layers of poly(styrene sulfonate)/poly(t-butyl styrene) (PtBS-PSS) adsorbed on both mica (hydrophilic) and octadecyltriethoxysilane (OTE) modified mica (hydrophobic). Normal compressing forces at two different constant grafting densities (bare and modified mica) were measured with the surface force apparatus and compared with theoretical prediction. The effect of salt concentration (Cs) upon the thickness of the self-assembled layers (Lo) was measured in each case. For adsorption of diblock copolymers onto OTE the resulting scaling relationship is much closer to the brush theory, Lo Cs-1/3. This result suggests that the adsorbed amount on mica is not high enough to form a brush.

[Polyelectrolyte microcapsules as systems for delivery of biologically active substances].

PubMed

Borodina, T N; Rumsh, L D; Kunizhev, S M; Sukhorukov, G B; Vorozhtsov, G N; Fel'dman, B M; Markvicheva, E A

2007-01-01

Novel biodegradable microcapsules for delivery of biologically active substances (BAS) were prepared by layer-by-layer (LbL) adsorption of oppositely charged polyelectrolytes, namely sodium alginate (Alg) and poly-L-lysine (PLL). To immobilize these BAS, porous spherical CaCO3 microparticles were used as templates. The templates (cores) were coated with several layers of oppositely charged polyelectrolytes forming shell on a core surface. The core-shell microparticles were converted into hollow microcapsules by a core dissolution after an EDTA treatment. Mild conditions for microcapsule fabrication allow to perform an entrapment of various biomolecules while keeping their bioactivity. Biocompatibility and biodegradable capability of the polyelectrolytes give a possibility to use the microcapsules as the target delivery systems. Chymotrypsin (Chym) entrapped into the microcapsules was used as a model enzyme. The immobilized enzyme was found to keep about 86% of the activity compared to a native Chym. The obtained microcapsules were stable at an acidic medium while they could be easily decomposed by trypsin treatment at an slightly alkaline medium. Chym was shown to be active after being released from the microcapsules decomposed by trypsin treatment. Thus, the microcapsules prepared by the LbL - technique can be used for the development of new type of BAS delivery systems in humans and animals.

From single Debye-Hückel chains to polyelectrolyte solutions: Simulation results

NASA Astrophysics Data System (ADS)

Kremer, Kurt

1996-03-01

This lecture will present results from simulations of single weakly charged flexible chains, where the electrostatic part of the interaction is modeled by a Debye-Hückel potential,( with U. Micka, IFF, Forschungszentrum Jülich, 52425 Jülich, Germany) as well as simulations of polyelectrolyte solutions, where the counterions are explicitly taken into account( with M. J. Stevens, Sandia Nat. Lab., Albuquerque, NM 87185-1111) ( M. J. Stevens, K. Kremer, JCP 103), 1669 (1995). The first set of the simulations is meant to clear a recent contoversy on the dependency of the persistence length LP on the screening length Γ. While the analytic theories give Lp ~ Γ^x with either x=1 or x=2, the simulations find for all experimentally accessible chain lengths a varying exponent, which is significantly smaller than 1. This causes serious doubts on the applicability of this model for weakly charged polyelectrolytes in general. The second part deals with strongly charged flexible polyelectrolytes in salt free solution. These simulations are performed for multichain systems. The full Coulomb interactions of the monomers and counterions are treated explicitly. Experimental measurements of the osmotic pressure and the structure factor are reproduced and extended. The simulations reveal a new picture of the chain structure based on calculations of the structure factor, persistence length, end-to-end distance, etc. Even at very low density, the chains show significant bending. Furthermore, the chains contract significantly before they start to overlap. We also show that counterion condensation dramatically alters the chain structure, even for a good solvent backbone.

Injection of polyelectrolytes enhances mobility of zero-valent iron nanoparticles in carbonate-rich porous media

NASA Astrophysics Data System (ADS)

Laumann, Susanne; Micić, Vesna; Schmid, Doris; Hofmann, Thilo

2013-04-01

The application of nanoscale zero-valent iron (nZVI) for in situ groundwater remediation has received increased attention as a beneficial and novel remediation technique. A precondition for effective nZVI field applications is its delivery to the contaminated source zones. This has proved to be difficult due to the limited mobility of nZVI, which remains one major obstacle to widespread utilization of this remediation approach (O'CAROLL ET AL., 2012). One important factor that controls mobility of nZVI is physical and chemical heterogeneity within the subsurface, such as mineralogical variations (KIM ET AL., 2012). In our previous study we showed that the nZVI transport in carbonate-rich porous media is significantly reduced compared to that in quartz porous media (LAUMANN ET AL., 2012). This is caused by favorable nZVI deposition onto carbonate sand and is attributed to the less negative surface charge of carbonate compared to that of quartz sand under the range of water chemical conditions typically encountered in aquifers. New strategies are therefore required to improve nZVI mobility in carbonate-rich porous media. One approach can be the injection of polyelectrolytes in the subsurface, which are expected to adsorb onto aquifer grains and provide greater repulsion between nZVI and the porous media. In this study the effect of co-injected polyelectrolytes on the transport of polyacrylic acid (PAA) coated nZVI in two model porous media, quartz and carbonate sands was evaluated. Column experiments were carried out aiming to evaluate mobility of PAA-nZVI co-injected with four polyelectrolytes, including natural organic matter (NOM), humic acid, carboxymethyl cellulose (CMC), and lignin sulfonate. The results demonstrated that the co-injection of the chosen polyelectrolytes does not influence mobility of PAA-nZVI in quartz sand; the breakthrough with co-injected polyelectrolytes was similar to that of the pure PAA-nZVI dispersion. This observation can be explained by the strong negative surface charge of the quartz sand, which was apparently not changed in the presence of polyelectrolytes. Conversely, the co-injected polyelectrolytes affected the breakthrough in carbonate sand, increasing nZVI mobility for approximately 15%. This can be explained by the attachment of the polyelectrolytes to the less negatively charged carbonate sand, which then promoted the PAA-nZVI mobility. Even though there are structural differences among the polyelectrolytes applied in this study, our results showed no significant variations in the PAA-nZVI mobility when these polyelectrolytes are present at concentration of 50 mg L-1. Lignin sulfonate was furthermore selected to investigate the effect of different polyelectrolyte concentrations (0, 10, 25, 50, 250, and 500 mg L-1) on the PAA-nZVI mobility. The results showed that higher lignin sulfonate concentrations (250 and 500 mg L-1) do not affect the transport of PAA-nZVI in quartz sand. In carbonate sand, on contrary, increasing mobility due to co-injected lignin sulfonate was observed at concentrations above 25 mg L-1, having the highest value with 500 mg L-1 co-injected with the PAA-nZVI dispersion. Overall, the results demonstrated that lignin sulfonate adsorption onto the carbonate sand reduce PAA-nZVI deposition onto aquifer grains and promote its mobility, the effect which is more pronounced at higher polyelectrolyte concentrations co-injected with the PAA-nZVI dispersion. The project is funded by the Federal Ministry of Agriculture, Forestry, Environment and Water Management (BMLFUW). Management by Kommunalkredit Public Consulting GmbH. Literature O'CAROLL, D. ET AL., (2012): Advances in Water Resources, in press. KIM, H.-J. ET AL., (2012): Journal of Colloid and Interface Science 370, 1-10. LAUMANN, S. ET AL., (2012): Environmental Pollution, submitted.

Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions.

PubMed

Haase, Martin F; Grigoriev, Dmitry; Moehwald, Helmuth; Tiersch, Brigitte; Shchukin, Dmitry G

2011-01-04

The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.

Copper diffusion and mechanical toughness at Cu-silica interfaces glued with polyelectrolyte nanolayers

NASA Astrophysics Data System (ADS)

Gandhi, D. D.; Singh, A. P.; Lane, M.; Eizenberg, M.; Ramanath, G.

2007-04-01

We demonstrate the use of polyallylamine hydrochloride (PAH)-polystyrene sulfonate (PSS) nanolayers to block Cu transport into silica. Cu/PSS-PAH/SiO2 structures show fourfold enhancement in device failure times during bias thermal annealing at 200 °C at an applied electric field of 2 MV/cm, when compared with structures with pristine Cu-SiO2 interfaces. Although the bonding at both Cu-PSS and PAH-SiO2 interfaces are strong, the interfacial toughness measured by the four-point bend tests is ˜2 Jm-2. Spectroscopic analysis of fracture surfaces reveals that weak electrostatic bonding at the PSS-PAH interface is responsible for the low toughness. Similar behavior is observed for Cu-SiO2 interfaces modified with other polyelectrolyte bilayers that inhibit Cu diffusion. Thus, while strong bonding at Cu-barrier and barrier-dielectric interfaces may be sufficient for blocking copper transport across polyelectrolyte bilayers, strong interlayer molecular bonding is a necessary condition for interface toughening. These findings are of importance for harnessing MNLs for use in future device wiring applications.

Cationic flocculants carrying hydrophobic functionalities: applications for solid/liquid separation.

PubMed

Schwarz, S; Jaeger, W; Paulke, B-R; Bratskaya, S; Smolka, N; Bohrisch, J

2007-07-26

The flocculation behaviors of three series of polycations with narrow molecular weight distributions carrying hydrophobic substituents on their backbones [poly(N-vinylbenzyl-N,N,N-trimethylammonium chloride), poly(N-vinylbenzyl-N,N-dimethyl-N-butylammonium chloride), and poly(N-vinylbenzylpyridinium chloride)] were investigated in dispersions of monodisperse polystyrene latexes and kaolin. Apparently, the charge density of the polycations decreases with increasing substituent hydrophobicity and increasing molecular weight of the polyelectrolytes. The necessary amount of flocculant for phase separation in dispersions with high substrate surface charge densities increases with increasing hydrophobicity of the polyelectrolyte. Nevertheless, the introduction of hydrophobic functionalities is beneficial, resulting in a substantial broadening of the range between the minimum and maximum amounts of flocculant necessary for efficient flocculation (flocculation window). An increase in ionic strength supports this effect. When the substrate has a low charge density, the hydrophobic interactions play a much more significant role in the flocculation process. Here, the minimum efficient doses remained the same for all three polyelectrolytes investigated, but the width of the flocculation window increased as the polycation hydrophobicity and the molecular weight increased. The necessary amount of flocculant increased with an increase in particle size at constant solid content of the dispersion, as well as with a decreasing number of particles at a constant particle size.

Designing carboxymethyl cellulose based layer-by-layer capsules as a carrier for protein delivery.

PubMed

Tripathy, Jasaswini; Raichur, Ashok M

2013-01-01

Stable hollow microcapsules composed of sodium carboxymethyl cellulose (CMC) and poly (allylamine hydrochloride) (PAH) were produced by layer-by-layer adsorption of polyelectrolytes onto CaCO(3) microparticles. Subsequently the core was removed by addition of chelating agents for calcium ions. Zeta potential studies showed charge reversal with deposition of successive polyelectrolyte layers, indicating that the alternate electrostatic adsorption of polyelectrolytes of opposite charge was successfully achieved. The size and surface morphology of the capsules was characterized by various microscopy techniques. The pH responsive loading behavior was elucidated by confocal laser scanning microscopy (CLSM) studies using fluorescence labeled dextran (FITC-dextran) and labeled BSA (FITC-BSA). CLSM images confirmed the open (pH≤6) and closed state (pH≥7) of the capsules. A model drug bovine serum albumin (BSA) was spontaneously loaded below its isoelectric point into hollow microcapsules, where BSA is positively charged. The loading of the BSA into the microcapsules was found to be dependent on the feeding concentration and pH of the medium. 65% of the loaded BSA was released over 7h of which about 34% was released in the first hour. These findings demonstrate that (CMC/PAH)(2) hollow capsules can be further exploited as a potential drug delivery system. Copyright © 2012 Elsevier B.V. All rights reserved.

Like-charged protein-polyelectrolyte complexation driven by charge patches

NASA Astrophysics Data System (ADS)

Yigit, Cemil; Heyda, Jan; Ballauff, Matthias; Dzubiella, Joachim

2015-08-01

We study the pair complexation of a single, highly charged polyelectrolyte (PE) chain (of 25 or 50 monomers) with like-charged patchy protein models (CPPMs) by means of implicit-solvent, explicit-salt Langevin dynamics computer simulations. Our previously introduced set of CPPMs embraces well-defined zero-, one-, and two-patched spherical globules each of the same net charge and (nanometer) size with mono- and multipole moments comparable to those of globular proteins with similar size. We observe large binding affinities between the CPPM and the like-charged PE in the tens of the thermal energy, kBT, that are favored by decreasing salt concentration and increasing charge of the patch(es). Our systematic analysis shows a clear correlation between the distance-resolved potentials of mean force, the number of ions released from the PE, and CPPM orientation effects. In particular, we find a novel two-site binding behavior for PEs in the case of two-patched CPPMs, where intermediate metastable complex structures are formed. In order to describe the salt-dependence of the binding affinity for mainly dipolar (one-patched) CPPMs, we introduce a combined counterion-release/Debye-Hückel model that quantitatively captures the essential physics of electrostatic complexation in our systems.

Inhibition of atherosclerosis-promoting microRNAs via targeted polyelectrolyte complex micelles

PubMed Central

Kuo, Cheng-Hsiang; Leon, Lorraine; Chung, Eun Ji; Huang, Ru-Ting; Sontag, Timothy J.; Reardon, Catherine A.; Getz, Godfrey S.; Tirrell, Matthew; Fang, Yun

2015-01-01

Polyelectrolyte complex micelles have great potential as gene delivery vehicles because of their ability to encapsulate charged nucleic acids forming a core by neutralizing their charge, while simultaneously protecting the nucleic acids from non-specific interactions and enzymatic degradation. Furthermore, to enhance specificity and transfection efficiency, polyelectrolyte complex micelles can be modified to include targeting capabilities. Here, we describe the design of targeted polyelectrolyte complex micelles containing inhibitors against dys-regulated microRNAs (miRNAs) that promote atherosclerosis, a leading cause of human mortality and morbidity. Inhibition of dys-regulated miRNAs in diseased cells associated with atherosclerosis has resulted in therapeutic efficacy in animal models and has been proposed to treat human diseases. However, the non-specific targeting of microRNA inhibitors via systemic delivery has remained an issue that may cause unwanted side effects. For this reason, we incorporated two different peptide sequences to our miRNA inhibitor containing polyelectrolyte complex micelles. One of the peptides (Arginine-Glutamic Acid-Lysine-Alanine or REKA) was used in another micellar system that demonstrated lesion-specific targeting in a mouse model of atherosclerosis. The other peptide (Valine-Histidine-Proline-Lysine-Glutamine-Histidine-Arginine or VHPKQHR) was identified via phage display and targets vascular endothelial cells through the vascular cell adhesion molecule-1 (VCAM-1). In this study we have tested the in vitro efficacy and efficiency of lesion- and cell-specific delivery of microRNA inhibitors to the cells associated with atherosclerotic lesions via peptide-targeted polyelectrolyte complex micelles. Our results show that REKA-containing micelles (fibrin-targeting) and VHPKQHR-containing micelles (VCAM-1 targeting) can be used to carry and deliver microRNA inhibitors into macrophages and human endothelial cells, respectively. Additionally, the functionality of miRNA inhibitors in cells was demonstrated by analyzing miRNA expression as well as the expression or the biological function of its downstream target protein. Our study provides the first demonstration of targeting dys-regulated miRNAs in atherosclerosis using targeted polyelectrolyte complex micelles and holds promising potential for translational applications. PMID:25685357

Cartilage-like electrostatic stiffening of responsive cryogel scaffolds

NASA Astrophysics Data System (ADS)

Offeddu, G. S.; Mela, I.; Jeggle, P.; Henderson, R. M.; Smoukov, S. K.; Oyen, M. L.

2017-02-01

Cartilage is a structural tissue with unique mechanical properties deriving from its electrically-charged porous structure. Traditional three-dimensional environments for the culture of cells fail to display the complex physical response displayed by the natural tissue. In this work, the reproduction of the charged environment found in cartilage is achieved using polyelectrolyte hydrogels based on polyvinyl alcohol and polyacrylic acid. The mechanical response and morphology of microporous physically-crosslinked cryogels are compared to those of heat-treated chemical gels made from the same polymers, as a result of pH-dependent swelling. In contrast to the heat-treated chemically-crosslinked gels, the elastic modulus of the physical cryogels was found to increase with charge activation and swelling, explained by the occurrence of electrostatic stiffening of the polymer chains at large charge densities. At the same time, the permeability of both materials to fluid flow was impaired by the presence of electric charges. This cartilage-like mechanical behavior displayed by responsive cryogels can be reproduced in other polyelectrolyte hydrogel systems to fabricate biomimetic cellular scaffolds for the repair of the tissue.

Molecular Dynamics Simulations of Adsorption of Poly(acrylic acid) and Poly(methacrylic acid) on Dodecyltrimethylammonium Chloride Micelle in Water: Effect of Charge Density.

PubMed

Sulatha, Muralidharan S; Natarajan, Upendra

2015-09-24

We have investigated the interaction of dodecyltrimethylammonium chloride (DoTA) micelle with weak polyelectrolytes, poly(acrylic acid) and poly(methacrylic acid). Anionic as well as un-ionized forms of the polyelectrolytes were studied. Polyelectrolyte-surfactant complexes were formed within 5-11 ns of the simulation time and were found to be stable. Association is driven purely by electrostatic interactions for anionic chains whereas dispersion interactions also play a dominant role in the case of un-ionized chains. Surfactant headgroup nitrogen atoms are in close contact with the carboxylic oxygens of the polyelectrolyte chain at a distance of 0.35 nm. In the complexes, the polyelectrolyte chains are adsorbed on to the hydrophilic micellar surface and do not penetrate into the hydrophobic core of the micelle. Polyacrylate chain shows higher affinity for complex formation with DoTA as compared to polymethacrylate chain. Anionic polyelectrolyte chains show higher interaction strength as compared to corresponding un-ionized chains. Anionic chains act as polymeric counterion in the complexes, resulting in the displacement of counterions (Na(+) and Cl(-)) into the bulk solution. Anionic chains show distinct shrinkage upon adsorption onto the micelle. Detailed information about the microscopic structure and binding characteristics of these complexes is in agreement with available experimental literature.

Improving Photocatalytic Activity through Electrostatic Self-Assembly: Polyelectrolytes as Tool for Solar Energy Conversion?

NASA Astrophysics Data System (ADS)

Groehn, Franziska

2015-03-01

With regard to the world's decreasing energy resources, developing strategies to exploit solar energy become more and more important. One approach is to take advantage of photocatalysis. Inspired by natural systems such as assemblies performing photosynthesis, it is highly promising to self-assemble synthetic functional species to form more effective or tailored supramolecular units. In this contribution, a new type of photocatalytically active self-assembled nanostructures in aqueous solution will be presented: supramolecular nano-objects obtained through self-assembly of macroions and multivalent organic or inorganic counterions. Polyelectrolyte-porphyrin nanoscale assemblies exhibit up to 10-fold higher photocatalytic activity than the corresponding porphyrins without polymeric template. Other self-assembled catalysts based on polyelectrolytes can exhibit expressed selectivity in a photocatalytic model reaction or even allow catalytic reactions in solution that are not possible with the building blocks only. Further, current results on combining different functional units at the polyelectrolyte template represent a next step towards more complex supramolecular structures for solar energy conversion.

Positively charged and bipolar layered poly(ether imide) nanofiltration membranes for water softening applications

NASA Astrophysics Data System (ADS)

Gassara, S.; Abdelkafi, A.; Quémener, D.; Amar, R. Ben; Deratani, A.

2015-07-01

Poly(ether imide) (PEI) ultrafiltration membranes were chemically modified with branched poly(ethyleneimine) to obtain nanofiltration (NF) membrane Cat PEI with a positive charge in the pH range below 9. An oppositely charged polyelectrolyte layer was deposited on the resulting membrane surface by using sodium polystyrene sulfonate (PSSNa) and sodium polyvinyl sulfonate (PVSNa) to prepare a bipolar layered membrane NF Cat PEI_PSS and Cat PEI_PVS having a negatively charged surface and positively charged pores. Cat PEI exhibited good performance to remove multivalent cations (more than 90% of Ca2+) from single salt solutions except in presence of sulfate ions. Adding an anionic polyelectrolyte layer onto the positively charged surface resulted in a significant enhancement of rejection performance even in presence of sulfate anions. Application of the prepared membranes in water softening of natural complex mixtures was successful for the different studied membranes and a large decrease of hardness was obtained. Moreover, Cat PEI_PSS showed a good selectivity for nitrate removal. Fouling experiments were carried out with bovine serum albumin, as model protein foulant. Cat PEI_PSS showed much better fouling resistance than Cat PEI with a quantitative flux recovery ratio.

Multifunctional Fe3O4@SiO2-Au Satellite Structured SERS Probe for Charge Selective Detection of Food Dyes.

PubMed

Sun, Zhenli; Du, Jingjing; Yan, Li; Chen, Shu; Yang, Zhilin; Jing, Chuanyong

2016-02-10

Nanofabrication of multifunctional surface-enhanced Raman scattering (SERS) substrates is strongly desirable but currently remains a challenge. The motivation of this study was to design such a substrate, a versatile core-satellite Fe3O4@SiO2-Au (FA) hetero-nanostructure, and demonstrate its use for charge-selective detection of food dye molecules as an exemplary application. Our experimental results and three-dimensional finite difference time domain (FDTD) simulation suggest that tuning the Au nanoparticle (NP) gap to sub-10 nm, which could be readily accomplished, substantially enhanced the Raman signals. Further layer-by-layer deposition of a charged polyelectrolyte on this magnetic SERS substrate induced active adsorption and selective detection of food dye molecules of opposite charge on the substrates. Molecular dynamics (MD) simulations suggest that the selective SERS enhancement could be attributed to the high affinity and close contact (within a 20 Å range) between the substrate and molecules. Density function theory (DFT) calculations confirm the charge transfer from food dye molecules to Au NPs via the polyelectrolytes. This multifunctional SERS platform provides easy separation and selective detection of charged molecules from complex chemical mixtures.

Rheology of polyelectrolyte complex materials

NASA Astrophysics Data System (ADS)

Tirrell, Matthew

Fluid polyelectrolyte complexes, sometimes known as complex coacervates, have rheological properties that are very sensitive to structure and salt concentration. Dynamic moduli of such viscoelastic materials very many orders of magnitude between solutions of no added salt to of order tenth molar salt, typical, for example of physiological saline. Indeed, salt plays a role in the rheology of complex coacervates analogous to that which temperature plays on polymer melts, leading to an empirical observation of what may be termed time-salt or frequency salt superposition. Block copolymers containing complexing ionic blocks also exhibit strong salt sensitivity of their rheological properties. Data representing these phenomena will be presented and discussed. Support from NIST, Department of Commerce, via the Center for Hierarchical Materials Design at Northwestern University and the University of Chicago is gratefully acknowledged.

Protein encapsulation via porous CaCO3 microparticles templating.

PubMed

Volodkin, Dmitry V; Larionova, Natalia I; Sukhorukov, Gleb B

2004-01-01

Porous microparticles of calcium carbonate with an average diameter of 4.75 microm were prepared and used for protein encapsulation in polymer-filled microcapsules by means of electrostatic layer-by-layer assembly (ELbL). Loading of macromolecules in porous CaCO3 particles is affected by their molecular weight due to diffusion-limited permeation inside the particles and also by the affinity to the carbonate surface. Adsorption of various proteins and dextran was examined as a function of pH and was found to be dependent both on the charge of the microparticles and macromolecules. The electrostatic effect was shown to govern this interaction. This paper discusses the factors which can influence the adsorption capacity of proteins. A new way of protein encapsulation in polyelectrolyte microcapsules is proposed exploiting the porous, biocompatible, and decomposable microparticles from CaCO3. It consists of protein adsorption in the pores of the microparticles followed by ELbL of oppositely charged polyelectrolytes and further core dissolution. This resulted in formation of polyelectrolyte-filled capsules with protein incorporated in interpenetrating polyelectrolyte network. The properties of CaCO3 microparticles and capsules prepared were characterized by scanning electron microscopy, microelectrophoresis, and confocal laser scanning microscopy. Lactalbumin was encapsulated by means of the proposed technique yielding a content of 0.6 pg protein per microcapsule. Horseradish peroxidase saves 37% of activity after encapsulation. However, the thermostability of the enzyme was improved by encapsulation. The results demonstrate that porous CaCO3 microparticles can be applied as microtemplates for encapsulation of proteins into polyelectrolyte capsules at neutral pH as an optimal medium for a variety of bioactive material, which can also be encapsulated by the proposed method. Microcapsules filled with encapsulated material may find applications in the field of biotechnology, biochemistry, and medicine.

Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

NASA Technical Reports Server (NTRS)

Shriver, D. F.; Ratner, M. A.; Vaynman, S.; Annan, K. O.; Snyder, J. F.

2003-01-01

Future NASA and Air Force missions require reliable and safe sources of energy with high specific energy and energy density that can provide thousands of charge-discharge cycles at more than 40% depth- of-discharge and that can operate at low temperatures. All solid-state batteries have substantial advantages with respect to stability, energy density, storage fife and cyclability. Among all solid-state batteries, those with flexible polymer electrolytes offer substantial advantages in cell dimensionality and commensurability, low temperature operation and thin film design. The above considerations suggest that lithium-polymer electrolyte systems are promising for high energy density batteries and should be the systems of choice for NASA and US Air Force applications. Polyelectrolytes (single ion conductors) are among most promising avenues for achieving a major breakthrough 'in the applicability of polymer- based electrolyte systems. Their major advantages include unit transference number for the cation, reduced cell polarization, minimal salt precipitation, and favorable electrolyte stability at interfaces. Our research is focused on synthesis, modeling and cell testing of single ion carriers, polyelectrolytes. During the first year of this project we attempted the synthesis of two polyelectrolytes. The synthesis of the first one, the poly(ethyleneoxide methoxy acrylateco-lithium 1,1,2-trifluorobutanesulfonate acrylate, was attempted few times and it was unsuccessful. We followed the synthetic route described by Cowie and Spence. The yield was extremely low and the final product could not be separated from the impurities. The synthesis of this polyelectrolyte is not described in this report. The second polyelectrolyte, comb polysiloxane polyelectrolyte containing oligoether and perfluoroether sidechains, was synthesized in sufficient quantity to study the range of properties such as thermal stability, Li- ion- conductivity and stability toward lithium metal. Also, the batteries containing this polyelectrolyte were assembled and tested. The results are detailed below. The synthesis of another polyelectrolyte similar to polysiloxane polyelectrolyte has been started, however, the synthesis was not completed due to termination of the project.

Development of Solid-State Nanopore Technology for Life Detection

NASA Technical Reports Server (NTRS)

Bywaters, K. B.; Schmidt, H.; Vercoutere, W.; Deamer, D.; Hawkins, A. R.; Quinn, R. C.; Burton, A. S.; Mckay, C. P.

2017-01-01

Biomarkers for life on Earth are an important starting point to guide the search for life elsewhere. However, the search for life beyond Earth should incorporate technologies capable of recognizing an array of potential biomarkers beyond what we see on Earth, in order to minimize the risk of false negatives from life detection missions. With this in mind, charged linear polymers may be a universal signature for life, due to their ability to store information while also inherently reducing the tendency of complex tertiary structure formation that significantly inhibit replication. Thus, these molecules are attractive targets for biosignature detection as potential "self-sustaining chemical signatures." Examples of charged linear polymers, or polyelectrolytes, include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) as well as synthetic polyelectrolytes that could potentially support life, including threose nucleic acid (TNA) and other xenonucleic acids (XNAs). Nanopore analysis is a novel technology that has been developed for singlemolecule sequencing with exquisite single nucleotide resolution which is also well-suited for analysis of polyelectrolyte molecules. Nanopore analysis has the ability to detect repeating sequences of electrical charges in organic linear polymers, and it is not molecule- specific (i.e. it is not restricted to only DNA or RNA). In this sense, it is a better life detection technique than approaches that are based on specific molecules, such as the polymerase chain reaction (PCR), which requires that the molecule being detected be composed of DNA.

The Structures of Fibronectin Adsorbed on Polyelectrolyte Thin Films

NASA Astrophysics Data System (ADS)

Shin, Kwanwoo; Satija, Sushil; Fang, Xiao-Hua; Li, Bin-Quan; Nadine, Pernodet; Miriam, Rafailovich; Sokolov, Jonathan; Arach, Goldar; Roser, Steve

2002-03-01

We have shown that it is possible to form a fibrilar network of fibronectin on a polyelectrolyte polymer film whose dimensions are similar to those reported on the extra cellular matrix. The fibronectin network was observed to form only when the charge density of the polymer was in excess of the natural charge density of the cell wall. Furthermore, the self-organized fibronectin layer was much thicker than the polymer film, indicating that long ranged interaction may play a key role in the assembly process. It is therefore important to understand the structure of the polymer layer/protein interface. Here we report on a neutron reflectivity study where we explore the structure of the polyelectrolyte layer, in this case sulfonated polystyrene (PSS_x.), with varying degree of sulfonation (x<30%), as a function of sulfur content and counter ion concentration. These results are then correlated with systemic study of the adsorption and the multilayer formation of fibronectin as a function of incubation time for various sulfonation levels of PSS_x. Furthermore, the surface charge on the substrates can be strongly influenced by the presence of salt ions, it is important to understand changes due to electrostatic interactions occurring in the various salt conditions. Complementary X-ray reflection was used to determine the salt density profile associating with the internal ionic polymer matrix. This work was funded in part of the NSF-MRSEC program.

Characterisation of capacitive field-effect sensors with a nanocrystalline-diamond film as transducer material for multi-parameter sensing.

PubMed

Abouzar, M H; Poghossian, A; Razavi, A; Williams, O A; Bijnens, N; Wagner, P; Schöning, M J

2009-01-01

The feasibility of a capacitive field-effect EDIS (electrolyte-diamond-insulator-semiconductor) platform for multi-parameter sensing is demonstrated by realising EDIS sensors with an O-terminated nanocrystalline-diamond (NCD) film as transducer material for the detection of pH and penicillin concentration as well as for the label-free electrical monitoring of adsorption and binding of charged macromolecules, like polyelectrolytes. The NCD films were grown on p-Si-SiO(2) substrates by microwave plasma-enhanced chemical vapour deposition. To obtain O-terminated surfaces, the NCD films were treated in an oxidising medium. The NCD-based field-effect sensors have been characterised by means of constant-capacitance method. The average pH sensitivity of the O-terminated NCD film was 40 mV/pH. A low detection limit of 5 microM and a high penicillin G sensitivity of 65-70 mV/decade has been obtained for an EDIS penicillin biosensor with the adsorptively immobilised enzyme penicillinase. Alternating potential changes, having tendency to decrease with increasing the number of adsorbed polyelectrolyte layers, have been observed after the layer-by-layer deposition of polyelectrolyte multilayers, using positively charged PAH (poly (allylamine hydrochloride)) and a negatively charged PSS (poly (sodium 4-styrene sulfonate)) as a model system. The response mechanism of the developed EDIS sensors is discussed.

Criticality and Connectivity in Macromolecular Charge Complexation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Jian; de Pablo, Juan J.

We examine the role of molecular connectivity and architecture on the complexation of ionic macromolecules (polyelectrolytes) of finite size. A unified framework is developed and applied to evaluate the electrostatic correlation free energy for point-like, rod-like, and coil-like molecules. That framework is generalized to molecules of variable fractal dimensions, including dendrimers. Analytical expressions for the free energy, correlation length, and osmotic pressure are derived, thereby enabling consideration of the effects of charge connectivity, fractal dimension, and backbone stiffness on the complexation behavior of a wide range of polyelectrolytes. Results are presented for regions in the immediate vicinity of the criticalmore » region and far from it. A transparent and explicit expression for the coexistence curve is derived in order to facilitate analysis of experimentally observed phase diagrams.« less

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles

DOE PAGES

Zhang, Honghu; Nayak, Srikanth; Wang, Wenjie; ...

2017-10-06

Here, we report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor–liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor–liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to themore » protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl 2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.« less

Renewable urea sensor based on a self-assembled polyelectrolyte layer.

PubMed

Wu, Zhaoyang; Guan, Lirui; Shen, Guoli; Yu, Ruqin

2002-03-01

A renewable urea sensor based on a carboxylic poly(vinyl chloride) (PVC-COOH) matrix pH-sensitive membrane has been proposed, in which a positively charged polyelectrolyte layer is first constructed by using a self-assembly technique on the surface of a PVC-COOH membrane, and urease, with negative charges, is then immobilized through electrostatic adsorption onto the PVC-COOH membrane, by controlling the pH of the urease solution below its isoelectric point. The response characteristics of the PVC-COOH pH-sensitive membrane and the effects of experimental conditions have been investigated in detail. Compared with conventional covalent immobilization, the urea sensor made with this self-assembly immobilization shows significant advantage in terms of sensitivity and ease of regeneration. The potential responses of the urea sensor with self-assembly immobilization increase with the urea concentration over the concentration range 10(-5) - 10(-1) mol l(-1), and the detection limit is 0.028 mmol(-1). Moreover, this type of urea sensor can be repeatedly regenerated by using a simple washing treatment with 0.01 mol l(-1) NaOH (containing 0.5 mol l(-1) NaCl) and 0.01 mol l(-1) HCl. The urease layers and the polyelectrolyte layers on the PVC-COOH membrane are removed, the potential response of the sensor to urea solutions of different concentrations returns nearly to zero, and another assembly cycle of urease and polyelectrolyte can then be carried out.

Polyelectrolyte-assisted preparation of gold nanocluster-doped silica particles with high incorporation efficiency and improved stability

NASA Astrophysics Data System (ADS)

Wang, Haonan; Huang, Zhenzhen; Guo, Zilong; Yang, Wensheng

2017-07-01

In this paper, we reported an approach for efficient incorporation of glutathione-capped gold nanoclusters (GSH-Au NCs) into silica particles with the assistance of a polyelectrolyte, poly-diallyldimethyl-ammoniumchloride (PDDA). In this approach, the negatively charged GSH-Au NCs were firstly mixed with the positively charged PDDA to form PDDA-Au NC complexes. Then, the complexes were added into a pre-hydrolyzed Stöber system to get the Au NCs-doped silica particles. With increased ratio of PDDA in the complexes, the negative charges on surface of the Au NCs were neutralized gradually and finally reversed to positive in presence of excess PDDA, which facilitated the incorporation of the Au NCs into the negatively charged silica matrix. Under the optimal amount of PDDA in the complexes, the incorporation efficiency of Au NCs could be as high as 88%. After being incorporated into the silica matrix, the Au NCs become much robust against pH and heavy metal ions attributed to the protection effect of silica and PDDA. This approach was also extendable to highly efficient incorporation of other negatively charged metal nanoclusters, such as bovine serum albumin-capped Cu nanoclusters, into silica matrix.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

Polyelectrolyte properties of single stranded DNA measured using SAXS and single molecule FRET: beyond the wormlike chain model

PubMed Central

Meisburger, Steve P.; Sutton, Julie L.; Chen, Huimin; Pabit, Suzette A.; Kirmizialtin, Serdal; Elber, Ron; Pollack, Lois

2013-01-01

Nucleic acids are highly charged polyelectrolytes that interact strongly with salt ions. Rigid, base-paired regions are successfully described with worm like chain models, but non base-paired single stranded regions have fundamentally different polymer properties because of their greater flexibility. Recently, attention has turned to single stranded nucleic acids due to the growing recognition of their biological importance, as well as the availability of sophisticated experimental techniques sensitive to the conformation of individual molecules. We investigate polyelectrolyte properties of poly(dT), an important and widely studied model system for flexible single stranded nucleic acids, in physiologically important mixed mono- and di-valent salt. We report measurements of the form factor and interparticle interactions using SAXS, end to end distances using smFRET, and number of excess ions using ASAXS. We present a coarse-grained model that accounts for flexibility, excluded volume, and electrostatic interactions in these systems. Predictions of the model are validated against experiment. We also discuss the state of all-atom, explicit solvent Molecular Dynamics simulations of poly(dT), the next step in understanding the complexities of ion interactions with these highly charged and flexible polymers. PMID:23606337

Molecular Dynamics Simulation of Salt Diffusion in Polyelectrolyte Assemblies.

PubMed

Zhang, Ran; Duan, Xiaozheng; Ding, Mingming; Shi, Tongfei

2018-06-05

The diffusion of salt ions and charged probe molecules in polyelectrolyte assemblies is often assumed to follow a theoretical hopping model, in which the diffusing ion is hopping between charged sites of chains based on electroneutrality. However, experimental verification of diffusing pathway at such microscales is difficult, and the corresponding molecular mechanisms remain elusive. In this study, we perform all-atom molecular dynamics (MD) simulations of salt diffusion in polyelectrolyte (PE) assembly of poly (sodium 4-styrenesulfonate) (PSS) and poly (diallyldimethylammonium chloride) (PDAC). Besides the ion hopping mode, the diffusing trajectories are found presenting common features of a jump process, i.e., subjecting to PE relaxation, water pockets in the structure open and close, thus the ion can move from one pocket to another. Anomalous subdiffusion of ions and water is observed due to the trapping scenarios in these water pockets. The jump events are much rarer compared with ion hopping but significantly increases salt diffusion with increasing temperature. Our result strongly indicates that salt diffusion in hydrated PDAC/PSS is a combined process of ion hopping and jump motion. This provides new molecular explanation for the coupling of salt motion with chain motion and the nonlinear increase of salt diffusion at glass transition temperature.

Electric Double Layer electrostatics of spherical polyelectrolyte brushes with pH-dependent charge density

NASA Astrophysics Data System (ADS)

Li, Hao; Chen, Guang; Sinha, Shayandev; Das, Siddhartha; Soft Matter, Interfaces,; Energy Laboratory (Smiel) Team

Understanding the electric double layer (EDL) electrostatics of spherical polyelectrolyte (PE) brushes, which are spherical particles grafted with PE layers, is essential for appropriate use of PE-grfated micro-nanoparticles for targeted drug delivery, oil recovery, water harvesting, emulsion stabilization, emulsion breaking, etc. Here we elucidate the EDL electrostatics of spherical PE brushes for the case where the PE exhibits pH-dependent charge density. This pH-dependence necessitates the consideration of explicit hydrogen ion concentration, which in turn dictates the distribution of monomers along the length of the grafted PE. This monomer distribution is shown to be a function of the nature of the sphere (metallic or a charged or uncharged dielectric or a liquid-filled sphere). All the calculations are performed for the case where the PE electrostatics can be decoupled from the PE elastic and excluded volume effects. Initial predictions are also provided for the case where such decoupling is not possible.

Noncovalent PEGylation through Protein-Polyelectrolyte Interaction: Kinetic Experiment and Molecular Dynamics Simulation.

PubMed

Kurinomaru, Takaaki; Kuwada, Kengo; Tomita, Shunsuke; Kameda, Tomoshi; Shiraki, Kentaro

2017-07-20

Noncovalent binding of polyethylene glycol (PEG) to a protein surface is a unique protein handling technique to control protein function and stability. A diblock copolymer containing PEG and polyelectrolyte chains (PEGylated polyelectrolyte) is a promising candidate for noncovalent attachment of PEG to a protein surface because of the binding through multiple electrostatic interactions without protein denaturation. To obtain a deeper understanding of protein-polyelectrolyte interaction at the molecular level, we investigated the manner in which cationic PEGylated polyelectrolyte binds to anionic α-amylase in enzyme kinetic experiments and molecular dynamics (MD) simulations. Cationic PEG-block-poly(N,N-dimethylaminoethyl) (PEG-b-PAMA) inhibited the enzyme activity of anionic α-amylase due to binding of PAMA chains. Enzyme kinetics revealed that the inhibition of α-amylase activity by PEG-b-PAMA is noncompetitive inhibition manner. In MD simulations, the PEG-b-PAMA molecule was initially located at six different placements of the x-, y-, and z-axis ±20 Å from the center of α-amylase, which showed that the PEG-b-PAMA nonspecifically bound to the α-amylase surface, corresponding to the noncompetitive inhibition manner that stems from the polymer binding to an enzyme surface other than the active site. In addition, the enzyme activity of α-amylase in the presence of PEG-b-PAMA was not inhibited by increasing the ionic strength, consistent with the MD simulation; i.e., PEG-b-PAMA did not interact with α-amylase in high ionic strength conditions. The results reported in this paper suggest that enzyme inhibition by PEGylated polyelectrolyte can be attributed to the random electrostatic interaction between protein and polyelectrolyte.

Surface modification for interaction study with bacteria and preosteoblast cells

NASA Astrophysics Data System (ADS)

Song, Qing

Surface modification plays a pivotal role in bioengineering. Polymer coatings can provide biocompatibility and biofunctionalities to biomaterials through surface modification. In this dissertation, initiated chemical vapor deposition (iCVD) was utilized to coat two-dimensional (2D) and three-dimensional (3D) substrates with differently charged polyelectrolytes in order to generate antimicrobial and osteocompatible biomaterials. ICVD is a modified CVD technique that enables surface modification in an all-dry condition without substrate damage and solvent contamination. The free-radical polymerization allows the vinyl polymers to conformally coat on various micro- and nano-structured substrates and maintains the delicate structure of the functional groups. The vapor deposition of polycations provided antimicrobial activity to planar and porous substrates through destroying the negatively charged bacterial membrane and brought about high contact-killing efficiency (99.99%) against Gram-positive Bacillus subtilis and Gram-negative Escherichia coli. Additionally, the polyampholytes synthesized by iCVD exhibited excellent antifouling performance against the adhesion of Gram-positive Listeria innocua and Gram-negative E. coli in phosphate buffered saline (PBS). Their antifouling activities were attributed to the electrostatic interaction and hydration layers that served as physical and energetic barriers to prevent bacterial adhesion. The contact-killing and antifouling polymers synthesized by iCVD can be applied to surface modification of food processing equipment and medical devices with the aim of reducing foodborne diseases and medical infections. Moreover, the charged polyelectrolyte modified 2D polystyrene surfaces displayed good osteocompatibility and enhanced osteogenesis of preosteoblast cells than the un-modified polystyrene surface. In order to promote osteoinduction of hydroxyapatite (HA) scaffolds, bioinspired polymer-controlled mineralization was conducted on the polyelectrolyte modified HA scaffolds. The mineralized scaffolds stimulated osteogenesis of preosteoblast cells compared with the control HA scaffolds. Therefore, the surface modification through vapor deposition of polyelectrolytes and polymer-controlled mineralization can improve osteoinduction of bone materials. In summary, the iCVD-mediated surface modification is a simple and promising approach to biofunctionalizing various structured substrates and generating antimicrobial and biocompatible biomaterials.

Brownian dynamics simulations of polyelectrolyte adsorption in shear flow with hydrodynamic interaction

NASA Astrophysics Data System (ADS)

Hoda, Nazish; Kumar, Satish

2007-12-01

The adsorption of single polyelectrolyte molecules in shear flow is studied using Brownian dynamics simulations with hydrodynamic interaction (HI). Simulations are performed with bead-rod and bead-spring chains, and electrostatic interactions are incorporated through a screened Coulombic potential with excluded volume accounted for by the repulsive part of a Lennard-Jones potential. A correction to the Rotne-Prager-Yamakawa tensor is derived that accounts for the presence of a planar wall. The simulations show that migration away from an uncharged wall, which is due to bead-wall HI, is enhanced by increases in the strength of flow and intrachain electrostatic repulsion, consistent with kinetic theory predictions. When the wall and polyelectrolyte are oppositely charged, chain behavior depends on the strength of electrostatic screening. For strong screening, chains get depleted from a region close to the wall and the thickness of this depletion layer scales as N1/3Wi2/3 at high Wi, where N is the chain length and Wi is the Weissenberg number. At intermediate screening, bead-wall electrostatic attraction competes with bead-wall HI, and it is found that there is a critical Weissenberg number for desorption which scales as N-1/2κ-3(lB∣σq∣)3/2, where κ is the inverse screening length, lB is the Bjerrum length, σ is the surface charge density, and q is the bead charge. When the screening is weak, adsorbed chains are observed to align in the vorticity direction at low shear rates due to the effects of repulsive intramolecular interactions. At higher shear rates, the chains align in the flow direction. The simulation method and results of this work are expected to be useful for a number of applications in biophysics and materials science in which polyelectrolyte adsorption plays a key role.

Magnetically aligned nanodomains: application in high-performance ion conductive membranes.

PubMed

Hasani-Sadrabadi, Mohammad Mahdi; Majedi, Fatemeh Sadat; Coullerez, Géraldine; Dashtimoghadam, Erfan; VanDersarl, Jules John; Bertsch, Arnaud; Moaddel, Homayoun; Jacob, Karl I; Renaud, Philippe

2014-05-28

Polyelectrolyte-coated magnetic nanoparticles were prepared by decorating the surface of superparamagnetic iron oxide nanoparticles (SPIONs) with crosslinked chitosan oligopolysaccharide (CS). These positively charged particles (CS-SPIONs) were then added to a negatively charged polymer (Nafion), and cast into membranes under an applied magnetic field. TEM and SAXS measurements confirmed this process created aligned, cylindrical nanodomains in the membranes. This was also indirectly confirmed by proton conductivity values. The strong electrostatic interaction between chitosan and Nafion prevented oxygen permeability and water evaporation at elevated temperatures through the proton conductive channels. The resultant proton exchange membranes showed lower conduction dependency to relative humidity, which is highly desirable for hydrogen fuel cells. The fuel cell performance tests were performed on the designed polyelectrolyte membrane by hydrogen-oxygen single cells at elevated temperature (120 °C) and low relative humidity.

Electro-actuated hydrogel walkers with dual responsive legs.

PubMed

Morales, Daniel; Palleau, Etienne; Dickey, Michael D; Velev, Orlin D

2014-03-07

Stimuli responsive polyelectrolyte hydrogels may be useful for soft robotics because of their ability to transform chemical energy into mechanical motion without the use of external mechanical input. Composed of soft and biocompatible materials, gel robots can easily bend and fold, interface and manipulate biological components and transport cargo in aqueous solutions. Electrical fields in aqueous solutions offer repeatable and controllable stimuli, which induce actuation by the re-distribution of ions in the system. Electrical fields applied to polyelectrolyte-doped gels submerged in ionic solution distribute the mobile ions asymmetrically to create osmotic pressure differences that swell and deform the gels. The sign of the fixed charges on the polyelectrolyte network determines the direction of bending, which we harness to control the motion of the gel legs in opposing directions as a response to electrical fields. We present and analyze a walking gel actuator comprised of cationic and anionic gel legs made of copolymer networks of acrylamide (AAm)/sodium acrylate (NaAc) and acrylamide/quaternized dimethylaminoethyl methacrylate (DMAEMA Q), respectively. The anionic and cationic legs were attached by electric field-promoted polyion complexation. We characterize the electro-actuated response of the sodium acrylate hydrogel as a function of charge density and external salt concentration. We demonstrate that "osmotically passive" fixed charges play an important role in controlling the bending magnitude of the gel networks. The gel walkers achieve unidirectional motion on flat elastomer substrates and exemplify a simple way to move and manipulate soft matter devices and robots in aqueous solutions.

Gating capacitive field-effect sensors by the charge of nanoparticle/molecule hybrids.

PubMed

Poghossian, Arshak; Bäcker, Matthias; Mayer, Dirk; Schöning, Michael J

2015-01-21

The semiconductor field-effect platform is a powerful tool for chemical and biological sensing with direct electrical readout. In this work, the field-effect capacitive electrolyte-insulator-semiconductor (EIS) structure - the simplest field-effect (bio-)chemical sensor - modified with citrate-capped gold nanoparticles (AuNPs) has been applied for a label-free electrostatic detection of charged molecules by their intrinsic molecular charge. The EIS sensor detects the charge changes in AuNP/molecule inorganic/organic hybrids induced by the molecular adsorption or binding events. The feasibility of the proposed detection scheme has been exemplarily demonstrated by realizing capacitive EIS sensors consisting of an Al-p-Si-SiO2-silane-AuNP structure for the label-free detection of positively charged cytochrome c and poly-d-lysine molecules as well as for monitoring the layer-by-layer formation of polyelectrolyte multilayers of poly(allylamine hydrochloride)/poly(sodium 4-styrene sulfonate), representing typical model examples of detecting small proteins and macromolecules and the consecutive adsorption of positively/negatively charged polyelectrolytes, respectively. For comparison, EIS sensors without AuNPs have been investigated, too. The adsorption of molecules on the surface of AuNPs has been verified via the X-ray photoelectron spectroscopy method. In addition, a theoretical model of the functioning of the capacitive field-effect EIS sensor functionalized with AuNP/charged-molecule hybrids has been discussed.

Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

PubMed

Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

2013-07-16

Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

Immobilization of Superoxide Dismutase on Polyelectrolyte-Functionalized Titania Nanosheets.

PubMed

Rouster, Paul; Pavlovic, Marko; Szilagyi, Istvan

2018-02-16

The superoxide dismutase (SOD) enzyme was successfully immobilized on titania nanosheets (TNS) functionalized with the poly(diallyldimethylammonium chloride) (PDADMAC) polyelectrolyte. The TNS-PDADMAC solid support was prepared by hydrothermal synthesis followed by self-assembled polyelectrolyte layer formation. It was found that SOD strongly adsorbed onto oppositely charged TNS-PDADMAC through electrostatic and hydrophobic interactions. The TNS-PDADMAC-SOD material was characterized by light scattering and microscopy techniques. Colloidal stability studies revealed that the obtained nanocomposites possessed good resistance against salt-induced aggregation in aqueous suspensions. The enzyme kept its functional integrity upon immobilization; therefore, TNS-PDADMAC-SOD showed excellent superoxide radical anion scavenging activity. The developed system is a promising candidate for applications in which suspensions of antioxidant activity are required in the manufacturing processes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyelectrolyte-Surfactant Complexes: A New Class of Organogelators

NASA Astrophysics Data System (ADS)

Cavicchi, Kevin; Liu, Yuqing; Guzman, Gustavo

2011-03-01

Polyelectrolyte-surfactant complexes (PE-SURFs) are a class of polymers generated by neutralizing a polyelectrolyte with an oppositely charged surfactant. It has been found that PE-SURFs composed of polystyrene sulfonate and long chain alkyl dimethyl amines act as good organogelators for a range of hydrophobic, organic solvents. Thermo-reversible organogels are formed by heating and cooling PE-SURF/solvent solutions. The gel transition temperature is influenced by the degree of polymerization, the length of the alkyl side-chain, the solubility parameter of the solvent, and the concentration of the gelator. Freeze-drying and scanning electron microscopy characterization of the resultant xerogels shows the formation of rod- and plate-like network morphologies depending on the system parameters. This behavior is consistent with gelation driven by the self-assembly of the amphiphilic PE-SURFs into micellar networks.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Abou-Kandil, Ahmed I; Caminade, Anne-Marie; Majoral, Jean-Pierre; Knoll, Wolfgang

2010-07-27

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

Simulation of weak polyelectrolytes: a comparison between the constant pH and the reaction ensemble method

NASA Astrophysics Data System (ADS)

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-03-01

The reaction ensemble and the constant pH method are well-known chemical equilibrium approaches to simulate protonation and deprotonation reactions in classical molecular dynamics and Monte Carlo simulations. In this article, we demonstrate the similarity between both methods under certain conditions. We perform molecular dynamics simulations of a weak polyelectrolyte in order to compare the titration curves obtained by both approaches. Our findings reveal a good agreement between the methods when the reaction ensemble is used to sweep the reaction constant. Pronounced differences between the reaction ensemble and the constant pH method can be observed for stronger acids and bases in terms of adaptive pH values. These deviations are due to the presence of explicit protons in the reaction ensemble method which induce a screening of electrostatic interactions between the charged titrable groups of the polyelectrolyte. The outcomes of our simulation hint to a better applicability of the reaction ensemble method for systems in confined geometries and titrable groups in polyelectrolytes with different pKa values.

Multi-Scale Structure of Coacervates formed by Oppositely Charged Polyelectrolytes

NASA Astrophysics Data System (ADS)

Rubinstein, Michael

We develop a scaling model of coacervates formed by oppositely charged polyelectrolytes and demonstrate that they self-organize into multi-scale structures. The intramolecular electrostatic interactions in dilute polyanion or polycation solutions are characterized by the electrostatic blobs with size D- and D+ respectively, that repel neighboring blobs on the same chains with electrostatic energy on the order of thermal energy kT . After mixing, electrostatic intramolecular repulsion of polyelectrolytes with higher charged density, say polyanions, keeps these polyanions in coacervates aligned into stretched arrays of electrostatic blobs of size D-

Gel phase formation in dilute triblock copolyelectrolyte complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

Gel phase formation in dilute triblock copolyelectrolyte complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

Gel phase formation in dilute triblock copolyelectrolyte complexes

DOE PAGES

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; ...

2017-02-23

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chainmore » aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Finally, our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.« less

Gel Phase Formation in Dilute Triblock Copolyelectrolyte Complexes

NASA Astrophysics Data System (ADS)

Srivastava, Samanvaya; Andreev, Marat; Prabhu, Vivek; de Pablo, Juan; Tirrell, Matthew

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at extremely low polymer concentrations (<1 % by mass) has been observed in scattering experiments and molecular dynamics simulations. In contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing polymer concentrations, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assemblies of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously upon solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of triblock copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries not only contribute to our fundamental understanding of the structure and pathways of complexation driven assemblies, but also raise intriguing prospects for formation of gel structures at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

Gel phase formation in dilute triblock copolyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

2017-02-01

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

Design of polyelectrolyte multilayer membranes for ion rejection and wastewater effluent treatment

NASA Astrophysics Data System (ADS)

Sanyal, Oishi

Polyelectrolyte multilayer (PEM) membranes present a special class of nanostructured membranes which have potential applications in a variety of water treatment operations. These membranes are fabricated by the layer-by-layer (LbL) assembly of alternately charged polyelectrolytes on commercial membrane surfaces. A large variety of polyelectrolytes and their varied deposition conditions (pH, number of bilayers etc.) allow very fine tuning of the membrane performance in terms of permeability and rejection. The first part of this thesis is about the application of PEM membranes to the removal of perchlorate ion from water. Being a monovalent ion, it is most effectively removed by a reverse osmosis (RO) membrane. However, these membranes inherently have very low fluxes which lead to high pressure requirements. In our work, we modified the surface of a nanofiltration (NF) membrane by the LbL assembly of oppositely charged polyelectrolytes. The appropriate tuning of the LbL conditions led to the development of a membrane with significantly higher flux than RO membranes but with equivalent perchlorate rejection. This was one of the best trade-offs offered by PEM membranes for monovalent ion rejection as has been reported in literature so far. While PEM membranes have mostly shown great potential in ion-rejection studies, they have seldom been tested for real wastewater effluents. The second part of this thesis, therefore, deals with evaluating the applicability of PEM membranes to treating an electrocoagulation (EC)-treated high strength wastewater. Two types of very commonly used polyelectrolyte combinations were tried out -- one of which was an ionically crosslinked system and the other one was covalently crosslinked. Both the types of PEM membranes showed a high level of COD reduction from the feed stream with higher fluxes than commercial RO membranes. One major challenge in using membranes for wastewater treatment is their fouling propensity. Like many other wastewater samples, the EC treated solution also contained a fair amount of organic foulants. These PEM membranes, however, indicated better anti-fouling properties than commercial NF/RO membranes under normal flow conditions. The last part of our work was focused on improving the anti-fouling properties of these membranes by the incorporation of clay nanoplatelets within polyelectrolyte multilayers. In this project, a commercial polyethersulfone (PES) membrane was modified by clay-polyelectrolyte composite thin films and tested against the EC effluent under tangential flow conditions. In comparison to the PEM membranes, these clay-PEM (c-PEM) hybrid membranes offered superior anti-fouling properties with higher fluxes and also required lesser number of layers. On crosslinking the polyelectrolytes, the c-PEM membranes yielded improved anti-fouling properties and high COD removal. Introduction of these inorganic nanoplatelets, however, led to a significant decline in the initial flux of the modified membranes as compared to bare PES membranes, which therefore necessitates further optimization. Some strategies which can potentially help in optimizing the performance of these c-PEM membranes have been discussed in this thesis.

Protein hydrogels with engineered biomolecular recognition

NASA Astrophysics Data System (ADS)

Mi, Lixin

Extracellular matrices (ECMs) are the hydrated macromolecular gels in which cells migrate and proliferate and organize into tissues in vivo . The development of artificial ECM with the required mechanical, physico-chemical, and biological properties has long been a challenge in the biomaterial research field. In this dissertation, a novel set of bioactive protein hydrogels has been synthesized and characterized at both molecular and materials levels. The self-recognized and self-assembled protein copolymers have the ability to provide engineered biofunctionality through the controlled arrangement of bioactive domains on the nanoscale. Genetic engineering methods have been employed to synthesize these protein copolymers. Plasmid DNA carrying genes to express both di- and tri-block proteins have been constructed using molecular cloning techniques. These genes were expressed in bacterial E. coli to ensure homogeneous protein length and anticipated structure. Three diblock protein sequences having a leucine zipper construct on one end and polyelectrolyte (AGAGAGPEG)10 on the other, have been studied by circular dichroism, size-exclusion chromatography, analytical ultracentrifugation, and static light scattering to characterize their secondary structure, structural stability, and oligomeric state. The results show that ABC diblock mixtures form very stable heterotrimer aggregates via self-recognition and self-assembly of the coiled coil end domains. Tri-block proteins with two leucine zipper motif ends flanking the polyelectrolyte random coil in the middle have been investigated by circular dichroism and fluorescence spectroscopy, and the hydrogels formed by self-assembly of these tri-blocks have been studied using transmission electronic microscopy and diffusing wave spectroscopy. The reversible gelation behavior is the result of heterotrimeric aggregation of helices to form the physical crosslinks in the gel, with the polyelectrolyte region center block retaining water soluble and swelling. The RGD cell adhesion tripeptide has been inserted into the polyelectrolyte region by site-directed mutagenesis. Two dimensional human foreskin fibroblast cultures have shown that the RGD-containing protein surface is bioactive in promoting cell attachment, cell signaling, and cytoskeleton organization. The protein and the cell recognize and interact at molecular level. Collectively, these findings indicate that this bioactive protein hydrogel system is a promising biomaterial for mammalian cell culture. This research may provide insights for the rational development of bioactive ECM for specific cell and tissue engineering applications.

Polyelectrolyte hydrogel instabilities in ionic solutions

NASA Astrophysics Data System (ADS)

English, Anthony E.; Tanaka, Toyoichi; Edelman, Elazer R.

1996-12-01

The phase behavior of polyelectrolyte hydrogels has been examined as a function of relative charge composition, bath salt concentration, and solvent quality. Nonlinear swelling instabilities of 2-hydroxyethyl methacrylate (HEMA) and methacrylic acid (MAAc) copolymer hydrogels manifested themselves as discontinuous first order swelling transitions as a function of bath salt concentration. A modified Flory-Huggins model was used to describe the regions of instability when bath salt concentration and solvent quality are considered as control variables. The role of ion dissociation equilibrium in the change from local or smooth transitions to nonlocal or discontinuous swelling transitions is illustrated within the framework of our model.

Charge-regularized swelling kinetics of polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Sen, Swati; Kundagrami, Arindam

The swelling kinetics of polyelectrolyte gels with fixed and variable degrees of ionization in salt-free solvent is studied by solving the constitutive equation of motion of the spatially and temporally varying displacement variable. Two methods for the swelling kinetics - the Bulk Modulus Method (BMM), which uses a linear stress-strain relationship (and, hence a bulk modulus), and the Stress Relaxation Method (SRM), which uses a phenomenological expression of osmotic stress, are explored to provide the spatio-temporal profiles for polymer density, osmotic stress, and degree of ionization, along with the time evolution of the gel size. Further, we obtain an analytical expression for the elastic modulus for linearized stress in the limit of small deformations. We match our theoretical profiles with the experiments of swelling of PNIPAM (uncharged) and Imidazolium-based (charged) minigels available in the literature. Ministry of Human Resource Development (MHRD), Government of India.

Environmentally friendly cellulose-based polyelectrolytes in wastewater treatment.

PubMed

Grenda, Kinga; Arnold, Julien; Gamelas, José A F; Rasteiro, Maria G

2017-09-01

Natural-based polyelectrolytes (PELs), with all the advantages coming from being produced from renewable and biodegradable sources, are a potential solution for the removal of dyes from wastewater. In this work, surplus Eucalyptus bleached cellulose fibres from a paper mill were modified to increase the charge and solubility of cellulose. First, reactive aldehyde groups were introduced in the cellulose backbone by periodate oxidation of cellulose. Further modification with alkylammonium produced positively charged cellulose-based PELs. The final products were characterized by several analytical techniques. The PEL with the highest substitution degree of cationic groups was evaluated for its performance in decolouration processes, bentonite being used as aid. This was found to be effective for colour removal of either anionic or cationic dyes. Bio-PELs can thus be considered as very favourable eco-friendly flocculation agents for decolouration of harsh effluents from several industries, considering their biodegradable nature and thus the ability to produce less sludge.

Photoinduced charge-transfer materials for nonlinear optical applications

DOEpatents

McBranch, Duncan W.

2006-10-24

A method using polyelectrolyte self-assembly for preparing multi-layered organic molecular materials having individual layers which exhibit ultrafast electron and/or energy transfer in a controlled direction occurring over the entire structure. Using a high molecular weight, water-soluble, anionic form of poly-phenylene vinylene, self-assembled films can be formed which show high photoluminescence quantum efficiency (QE). The highest emission QE is achieved using poly(propylene-imine) (PPI) dendrimers as cationic binders. Self-quenching of the luminescence is observed as the solid polymer film thickness is increased and can be reversed by inserting additional spacer layers of transparent polyelectrolytes between each active conjugated layer, such that the QE grows with thickness. A red shift of the luminescence is also observed as additional PPV layers are added. This effect persists as self-quenching is eliminated. Charge transfer superlattices can be formed by additionally incorporating C.sub.60 acceptor layers.

A novel system for water soluble protein encapsulation with high efficiency: "micelles enhanced" polyelectrolyte capsules.

PubMed

Li, Xiaodong; Li, Xiaohui; Zhang, Jianxiang; Zhao, Shifang; Shen, Jiacong

2008-06-01

Novel "micelles enhanced" polyelectrolyte (PE) capsules based on functional templates of hybrid calcium carbonate were fabricated. Evidences suggested that the structure of capsule wall was different from that of conventional PE capsules, and the wall permeability of these PE capsules changed significantly. Lysozyme, a positively charged protein in neutral solution, was studied as a model protein to be encapsulated into the "micelles enhanced" PE capsules. Confocal laser scanning microscope was used to observe the entrapping process in real time, while UV-Vis spectroscope and scanning force microscope measurements suggested the high efficiency of encapsulation. In addition, the fluorescence recovery after photobleaching technique was employed to determine the existence form of deposited molecules. Further studies showed even negatively charged water-soluble peptides or proteins can be encapsulated into these hybrid capsules by modulating the pH value in bulk solution under its isoelectronic point as well. Copyright 2007 Wiley Periodicals, Inc.

Single molecule spectroscopy reveals heterogeneous transport mechanisms for molecular ions in a polyelectrolyte polymer brush.

PubMed

Reznik, Carmen; Estillore, Nicel; Advincula, Rigoberto C; Landes, Christy F

2009-11-05

Single molecule polarization and fluorescence correlation spectroscopy were used to evaluate heterogeneous transport mechanisms of molecular ions within supported polyelectrolyte brushes. Modes of diffusive transport include periods of significantly restricted rotational motion, often maintained over tens of milliseconds; periods of fast molecular rotation; and occasional adsorption of fluorescent probe molecules in the brush. The studies reveal rapid switching between orientational states during each observed mode of motion. Through quantitative analysis of state occupation times, the rate constants for transitions from weakly associated to strongly associated states were extracted. Additionally, the pH dependence of the ion transport rates in the brush exhibits an abrupt, rather than continuous, trend. These single molecule studies demonstrate the presence of dynamic anisotropic interactions between the charged molecular probe and the polymer brush and provide experimental evidence of stimuli responsive switchable transport functionality in the polyelectrolyte brush.

A bead-spring chain as a one-dimensional polyelectrolyte gel.

PubMed

Manning, Gerald S

2018-05-23

The physical principles underlying expansion of a single-chain polyelectrolyte coil caused by Coulomb repulsions among its ionized groups, and the expansion of a cross-linked polyelectrolyte gel, are probably the same. In this paper, we analyze a "one-dimensional" version of a gel, namely, a linear chain of charged beads connected by Hooke's law springs. In the Debye-Hückel range of relatively weak Coulomb strength, where counterion condensation does not occur, the springs are realistically stretched on a nanolength scale by the repulsive interactions among the beads, if we use a spring constant normalized by the inverse square of the solvent Bjerrum length. The persistence length and radius of gyration counter-intuitively decrease when Coulomb strength is increased, if analyzed in the framework of an OSF-type theory; however, a buckling theory generates the increase that is consistent with bead-spring simulations.

Origin of translocation barriers for polyelectrolyte chains.

PubMed

Kumar, Rajeev; Muthukumar, M

2009-11-21

For single-file translocations of a charged macromolecule through a narrow pore, the crucial step of arrival of an end at the pore suffers from free energy barriers, arising from changes in intrachain electrostatic interaction, distribution of ionic clouds and solvent molecules, and conformational entropy of the chain. All contributing factors to the barrier in the initial stage of translocation are evaluated by using the self-consistent field theory for the polyelectrolyte and the coupled Poisson-Boltzmann description for ions without radial symmetry. The barrier is found to be essentially entropic due to conformational changes. For moderate and high salt concentrations, the barriers for the polyelectrolyte chain are quantitatively equivalent to that of uncharged self-avoiding walks. Electrostatic effects are shown to increase the free energy barriers, but only slightly. The degree of ionization, electrostatic interaction strength, decreasing salt concentration, and the solvent quality all result in increases in the barrier.

Altering surface charge nonuniformity on individual colloidal particles.

PubMed

Feick, Jason D; Chukwumah, Nkiru; Noel, Alexandra E; Velegol, Darrell

2004-04-13

Charge nonuniformity (sigmazeta) was altered on individual polystyrene latex particles and measured using the novel experimental technique of rotational electrophoresis. It has recently been shown that unaltered sulfated latices often have significant charge nonuniformity (sigmazeta = 100 mV) on individual particles. Here it is shown that anionic polyelectrolytes and surfactants reduce the native charge nonuniformity on negatively charged particles by 80% (sigmazeta = 20 mV), even while leaving the average surface charge density almost unchanged. Reduction of charge uniformity occurs as large domains of nonuniformity are minimized, giving a more random distribution of charge on individual particle surfaces. Targeted reduction of charge nonuniformity opens new opportunities for the dispersion of nanoparticles and the oriented assembly of particles.

Design strategy of pH-sensitive triblock copolymer micelles for efficient cellular uptake by computer simulations

NASA Astrophysics Data System (ADS)

Xia, Qiang-sheng; Ding, Hong-ming; Ma, Yu-qiang

2018-03-01

Efficient delivery of nanoparticles into specific cell interiors is of great importance in biomedicine. Recently, the pH-responsive micelle has emerged as one potential nanocarrier to realize such purpose since there exist obvious pH differences between normal tissues and tumors. Herein, by using dissipative particle dynamics simulation, we investigate the interaction of the pH-sensitive triblock copolymer micelles composed of ligand (L), hydrophobic block (C) and polyelectrolyte block (P) with cell membrane. It is found that the structure rearrangement of the micelle can facilitate its penetration into the lower leaflet of the bilayer. However, when the ligand-receptor specific interaction is weak, the micelles may just fuse with the upper leaflet of the bilayer. Moreover, the ionization degree of polyelectrolyte block and the length of hydrophobic block also play a vital role in the penetration efficiency. Further, when the sequence of the L, P, C beads in the copolymers is changed, the translocation pathways of the micelles may change from direct penetration to Janus engulfment. The present study reveals the relationship between the molecular structure of the copolymer and the uptake of the pH-sensitive micelles, which may give some significant insights into the experimental design of responsive micellar nanocarriers for highly efficient cellular delivery.

Surfactant mediated polyelectrolyte self-assembly

DOE PAGES

Goswami, Monojoy; Borreguero Calvo, Jose M.; Pincus, Phillip A.; ...

2015-11-25

Self-assembly and dynamics of polyelectrolyte (PE) surfactant complex (PES) is investigated using molecular dynamics simulations. The complexation is systematically studied for five different PE backbone charge densities. At a fixed surfactant concentration the PES complexation exhibits pearl-necklace to agglomerated double spherical structures with a PE chain decorating the surfactant micelles. The counterions do not condense on the complex, but are released in the medium with a random distribution. The relaxation dynamics for three different length scales, polymer chain, segmental and monomer, show distinct features of the charge and neutral species; the counterions are fastest followed by the PE chain andmore » surfactants. The surfactant heads and tails have the slowest relaxation due to their restricted movement inside the agglomerated structure. At the shortest length scale, all the charge and neutral species show similar relaxation dynamics confirming Rouse behavior at monomer length scales. Overall, the present study highlights the structure-property relationship for polymer-surfactant complexation. These results will help improve the understanding of PES complex and should aid in the design of better materials for future applications.« less

DNA - peptide polyelectrolyte complexes: Phase control by hybridization

NASA Astrophysics Data System (ADS)

Vieregg, Jeffrey; Lueckheide, Michael; Marciel, Amanda; Leon, Lorraine; Tirrell, Matthew

DNA is one of the most highly-charged molecules known, and interacts strongly with charged molecules in the cell. Condensation of long double-stranded DNA is one of the classic problems of biophysics, but the polyelectrolyte behavior of short and/or single-stranded nucleic acids has attracted far less study despite its importance for both biological and engineered systems. We report here studies of DNA oligonucleotides complexed with cationic peptides and polyamines. As seen previously for longer sequences, double-stranded oligonucleotides form solid precipitates, but single-stranded oligonucleotides instead undergo liquid-liquid phase separation to form coacervate droplets. Complexed oligonucleotides remain competent for hybridization, and display sequence-dependent environmental response. We observe similar behavior for RNA oligonucleotides, and methylphosphonate substitution of the DNA backbone indicates that nucleic acid charge density controls whether liquid or solid complexes are formed. Liquid-liquid phase separations of this type have been implicated in formation of membraneless organelles in vivo, and have been suggested as protocells in early life scenarios; oligonucleotides offer an excellent method to probe the physics controlling these phenomena.

Swelling characteristics of acrylic acid polyelectrolyte hydrogel in a dc electric field

NASA Astrophysics Data System (ADS)

Jabbari, Esmaiel; Tavakoli, Javad; Sarvestani, Alireza S.

2007-10-01

A novel application of environmentally sensitive polyelectrolytes is in the fabrication of BioMEMS devices as sensors and actuators. Poly(acrylic acid) (PAA) gels are anionic polyelectrolyte networks that exhibit volume expansion in aqueous physiological environments. When an electric field is applied to PAA polyelectrolyte gels, the fixed anionic polyelectrolyte charges and the requirement of electro-neutrality in the network generate an osmotic pressure, above that in the absence of the electric field, to expand the network. The objective of this research was to investigate the effect of an externally applied dc electric field on the volume expansion of the PAA polyelectrolyte gel in a simulated physiological solution of phosphate buffer saline (PBS). For swelling studies in the electric field, two platinum-coated plates, as electrodes, were wrapped in a polyethylene sheet to protect the plates from corrosion and placed vertically in a vessel filled with PBS. The plates were placed on a rail such that the distance between the two plates could be adjusted. The PAA gel was synthesized by free radical crosslinking of acrylic acid monomer with ethylene glycol dimethacrylate (EGDMA) crosslinker. Our results demonstrate that volume expansion depends on the intensity of the electric field, the PAA network density, network homogeneity, and the position of the gel in the field relative to positive/negative electrodes. Our model predictions for PAA volume expansion, based on the dilute electrolyte concentration in the gel network, is in excellent agreement with the experimental findings in the high-electric-field regime (250-300 Newton/Coulomb).

Charge-regularized swelling kinetics of polyelectrolyte gels: Elasticity and diffusion

NASA Astrophysics Data System (ADS)

Sen, Swati; Kundagrami, Arindam

2017-11-01

We apply a recently developed method [S. Sen and A. Kundagrami, J. Chem. Phys. 143, 224904 (2015)], using a phenomenological expression of osmotic stress, as a function of polymer and charge densities, hydrophobicity, and network elasticity for the swelling of spherical polyelectrolyte (PE) gels with fixed and variable charges in a salt-free solvent. This expression of stress is used in the equation of motion of swelling kinetics of spherical PE gels to numerically calculate the spatial profiles for the polymer and free ion densities at different time steps and the time evolution of the size of the gel. We compare the profiles of the same variables obtained from the classical linear theory of elasticity and quantitatively estimate the bulk modulus of the PE gel. Further, we obtain an analytical expression of the elastic modulus from the linearized expression of stress (in the small deformation limit). We find that the estimated bulk modulus of the PE gel decreases with the increase of its effective charge for a fixed degree of deformation during swelling. Finally, we match the gel-front locations with the experimental data, taken from the measurements of charged reversible addition-fragmentation chain transfer gels to show an increase in gel-size with charge and also match the same for PNIPAM (uncharged) and imidazolium-based (charged) minigels, which specifically confirms the decrease of the gel modulus value with the increase of the charge. The agreement between experimental and theoretical results confirms general diffusive behaviour for swelling of PE gels with a decreasing bulk modulus with increasing degree of ionization (charge). The new formalism captures large deformations as well with a significant variation of charge content of the gel. It is found that PE gels with large deformation but same initial size swell faster with a higher charge.

Polyelectrolytes with high charge density

NASA Technical Reports Server (NTRS)

Rembaum, A.; Yen, S. P. S.

1974-01-01

Polymers can be used as flocculants to clarify residential and industrial water supplies and as bactericidal and fungicidal agents. They can be used in preparation of electroconductive photocopy papers, to improve living cell adhesion to glass or plastic, and as anticancer agents.

Specific interactions versus counterion condensation. 2. Theoretical treatment within the counterion condensation theory.

PubMed

Donati, Ivan; Benegas, Julio C; Cesàro, Attilio; Paoletti, Sergio

2006-05-01

Polyuronates such as pectate and alginate are very well-known examples of biological polyelectrolytes undergoing, upon addition of divalent cations, an interchain association that acts as the junction of an eventually formed stable hydrogel. In the present paper, a thermodynamic model based on the counterion condensation theory has been developed to account for this cation-induced chain pairing of negatively charged polyelectrolytes. The strong interactions between cross-linking ions and uronate moieties in the specific binding site have been described in terms of chemical bonding, with complete charge annihilation between the two species. The chain-pairing process is depicted as progressively increasing with the concentration of cross-linking counterions and is thermodynamically defined by the fraction of each species. On these bases, the total Gibbs energy of the system has been expressed as the sum of the contributions of the Gibbs energy of the (single) chain stretches and of the (associated) dimers, weighted by their respective fractions 1 - theta and theta. In addition, the model assumes that the condensed divalent counterions exhibit an affinity free-energy for the chain, G(C)(aff,0), and the junction, G(D)(aff,0), respectively. Moreover, a specific Gibbs energy of chemical bonding, G(bond,0), has been introduced as the driving force for the formation of dimers. The model provides the mathematical formalism for calculating the fraction, theta, of chain dimers formed and the amount of ions condensed and bound onto the polyelectrolyte when two different types of counterions (of equal or different valence) are present. The effect of the parameter G(bond,0) has been investigated and, in particular, its difference from G(C,D)(aff,0) was found to be crucial in determining the distribution of the ions into territorial condensation and chemical bonding, respectively. Finally, the effect of the variation of the molar ratio between cross-linking ions and uronic groups in the specific binding sites, sigma0, was evaluated. In particular, a remarkable decrease in the amount of condensed counterions has been pointed out in the case of sigma0 = 1/3, with respect to the value of sigma0 = 1/4, characterizing the traditional "egg-box" structure, as a result of the drop of the charge density of the polyelectrolyte induced by complete charge annihilation.

Single-chain-in-mean-field simulations of weak polyelectrolyte brushes

NASA Astrophysics Data System (ADS)

Léonforte, F.; Welling, U.; Müller, M.

2016-12-01

Structural properties of brushes which are composed of weak acidic and basic polyelectrolytes are studied in the framework of a particle-based approach that implicitly accounts for the solvent quality. Using a semi-grandcanonical partition function in the framework of the Single-Chain-in-Mean-Field (SCMF) algorithm, the weak polyelectrolyte is conceived as a supramolecular mixture of polymers in different dissociation states, which are explicitly treated in the partition function and sampled by the SCMF procedure. One obtains a local expression for the equilibrium acid-base reaction responsible for the regulation of the charged groups that is also incorporated to the SCMF sampling. Coupled to a simultaneous treatment of the electrostatics, the approach is shown to capture the main features of weak polyelectrolyte brushes as a function of the bulk pH in the solution, the salt concentration, and the grafting density. Results are compared to experimental and theoretical works from the literature using coarse-grained representations of poly(acrylic acid) (PAA) and poly(2-vinyl pyridine) (P2VP) polymer-based brushes. As the Born self-energy of ions can be straightforwardly included in the numerical approach, we also study its effect on the local charge regulation mechanism of the brush. We find that its effect becomes significant when the brush is dense and exposed to high salt concentrations. The numerical methodology is then applied (1) to the study of the kinetics of collapse/swelling of a P2VP brush and (2) to the ability of an applied voltage to induce collapse/swelling of a PAA brush in a pH range close to the pKa value of the polymer.

Polyelectrolyte multi-layers assembly of SiCHA nanopowders and collagen type I on aminolysed PLA films to enhance cell-material interactions.

PubMed

Baba Ismail, Yanny Marliana; Ferreira, Ana Marina; Bretcanu, Oana; Dalgarno, Kenneth; El Haj, Alicia J

2017-11-01

This paper presents a new approach in assembling bone extracellular matrix components onto PLA films, and investigates the most favourable environment which can be created using the technique for cell-material interactions. Poly (lactic acid) (PLA) films were chemically modified by covalently binding the poly(ethylene imine) (PEI) as to prepare the substrate for immobilization of polyelectrolyte multilayers (PEMs) coating. Negatively charged polyelectrolyte consists of well-dispersed silicon-carbonated hydroxyapatite (SiCHA) nanopowders in hyaluronic acid (Hya) was deposited onto the modified PLA films followed by SiCHA in collagen type I as the positively charged polyelectrolyte. The outermost layer was finally cross-linked by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrocholoride and N-hydroxysulfosuccinimide sodium salt (EDC/NHS) solutions. The physicochemical features of the coated PLA films were monitored via X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscope (AFM). The amounts of calcium and collagen deposited on the surface were qualitatively and quantitatively determined. The surface characterizations suggested that 5-BL has the optimum surface roughness and highest amounts of calcium and collagen depositions among tested films. In vitro human mesenchymal stem cells (hMSCs) cultured on the coated PLA films confirmed that the coating materials greatly improved cell attachment and survival compared to unmodified PLA films. The cell viability, cell proliferation and Alkaline Phosphatase (ALP) expression on 5-BL were found to be the most favourable of the tested films. Hence, this newly developed coating materials assembly could contribute to the improvement of the bioactivity of polymeric materials and structures aimed to bone tissue engineering applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Electroosmotic velocity in an array of parallel soft cylinders in a salt-free medium.

PubMed

Ohshima, Hiroyuki

2004-11-15

A theory of electroosmosis in an array of parallel soft cylinders (i.e. polyelectrolyte-coated cylinders) in a salt-free medium is presented. It is shown that there is a certain critical value of the particle charge and that if the particle charge is greater than the critical value, then the electroosmotic velocity becomes constant independent of the particle charge due to the counterion condensation effects, as in the case of other electrokinetic phenomena in salt-free media.

Humic substance charge determination by titration with a flexible cationic polyelectrolyte

NASA Astrophysics Data System (ADS)

Tan, Wen-Feng; Norde, Willem; Koopal, Luuk K.

2011-10-01

The anionic charge of humic substances (HS) plays a major role in the interaction of HS with other components. Therefore, the potential of the polyelectrolyte titration technique to obtain the charge density of HS in simple 1-1 electrolyte solutions has been investigated. Titrations are carried out with an automatic titrator combined with the "Mütek particle charge detector" which allows determination of the Mütek potential and the pH as a function of the added amount of titrant which is a solution of poly-diallyldimethylammonium chloride (polyDADMAC), a cationic strong polyelectrolyte. When the Mütek potential reverses its sign the iso-electric point (IEP) of the polyDADMAC-HS complex is reached. The polyDADMAC/HS mass ratio at the IEP gives information on the HS charge density and from the pH changes in solution an estimate of the charge regulation in the HS-polyDADMAC complex can be obtained. In general, for polyDADMAC-HS complexes an increase in the dissociation of the acid groups of HS is found (charge regulation). The charge regulation decreases with increasing concentration of 1-1 background electrolyte. Cation incorporation can be neglected at 1-1 electrolyte concentrations ⩽ 1 mmol L -1 and a 1-1 stoichiometry exists between the polyDADMAC and HS charge. However, at these low salt concentrations the charge regulation is substantial. A detailed analysis of purified Aldrich humic acid (PAHA) at pH 5 and a range of KCl concentrations reveals that the anionic charge of PAHA in the complex increases at 5 mmol L -1 KCl by 30% and at 150 mmol L -1 KCl by 12%. On the other hand, increasing amounts of K + become incorporated in the complex: at 5 mmol L -1 KCl 5% and at 150 mmol L -1 KCl 24% of the PAHA charge is balanced by K +. By comparing at pH 5 the mass ratios polyDADMAC/PAHA in the complex at the IEP with the theoretical mass ratios of polyDADMAC/PAHA required to neutralize PAHA in the absence of charge regulation and K + incorporation, it is found that at 50 mmol L -1 KCl the extra negative charge due to the interaction between polyDADMAC and PAHA is just compensated by K + incorporation in the complex. Therefore, a pseudo 1-1 stoichiometry exists at about 50 mmol L -1 1-1 electrolyte concentration and only at this salt concentration polyDADMAC titrations and conventional proton titrations give identical results. Most likely this is also true for other HA samples and other pH values. For FA further study is required to reveal the conditions for which polyDADMAC and proton titrations give identical results.

Complex coacervation in charge complementary biopolymers: Electrostatic versus surface patch binding.

PubMed

Pathak, Jyotsana; Priyadarshini, Eepsita; Rawat, Kamla; Bohidar, H B

2017-12-01

In this review, a number of systems are described to demonstrate the effect of polyelectrolyte chain stiffness (persistence length) on the coacervation phenomena, after we briefly review the field. We consider two specific types of complexation/coacervation: in the first type, DNA is used as a fixed substrate binding to flexible polyions such as gelatin A, bovine serum albumin and chitosan (large persistence length polyelectrolyte binding to low persistence length biopolymer), and in the second case, different substrates such as gelatin A, bovine serum albumin, and chitosan were made to bind to a polyion gelatin B (low persistence length substrate binding to comparable persistence length polyion). Polyelectrolyte chain flexibility was found to have remarkable effect on the polyelectrolyte-protein complex coacervation. The competitive interplay of electrostatic versus surface patch binding (SPB) leading to associative interaction followed by complex coacervation between these biopolymers is elucidated. We modelled the SPB interaction in terms of linear combination of attractive and repulsive Coulombic forces with respect to the solution ionic strength. The aforesaid interactions were established via a universal phase diagram, considering the persistence length of polyion as the sole independent variable. Copyright © 2017 Elsevier B.V. All rights reserved.

Small‐angle X‐ray scattering as a useful supplementary technique to determine molecular masses of polyelectrolytes in solution

PubMed Central

Plazzotta, Beatrice; Diget, Jakob Stensgaard; Zhu, Kaizheng; Nyström, Bo

2016-01-01

ABSTRACT Determination of molecular masses of charged polymers is often nontrivial and most methods have their drawbacks. For polyelectrolytes, a new possibility for the determination of number‐average molecular masses is represented by small‐angle X‐ray scattering (SAXS) which allows fast determinations with a 10% accuracy. This is done by relating the mass to the position of a characteristic peak feature which arises in SAXS due to the local ordering caused by charge‐repulsions between polyelectrolytes. Advantages of the technique are the simplicity of data analysis, the independency from polymer architecture, and the low sample and time consumption. The method was tested on polyelectrolytes of various structures and chemical compositions, and the results were compared with those obtained from more conventional techniques, such as asymmetric flow field‐flow fractionation, gel permeation chromatography, and classical SAXS data analysis, showing that the accuracy of the suggested method is similar to that of the other techniques. © 2016 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1913–1917 PMID:27840558

Alternating current electroosmotic flow in polyelectrolyte-grafted nanochannel.

PubMed

Li, Fengqin; Jian, Yongjun; Chang, Long; Zhao, Guangpu; Yang, Liangui

2016-11-01

In this work, we investigate the time periodic electroosmotic flow (EOF) of an electrolyte solution through a slit polyelectrolyte-grafted (PE-grafted) nanochannel under applied alternating current (AC) electrical field. The PE-grafted nanochannel is represented by a rigid surface covered by a polyelectrolyte layer (PEL) in a brush-like configuration. Under Debye-Hückel approximation, we obtain analytical solutions of electrical potential in decoupled regime of PE-grafted nanochannel, where the thickness of PEL is independent of the electrostatic effects triggered by polyelectrolyte charges. Based upon the electrical potential obtained above, we calculate EOF velocities with uniform and non-uniform drag coefficients for PE-grafted nanochannel and compare their results. The effects of pertinent dimensionless parameters on EOF velocity amplitude are discussed in detail. Moreover, the amplitude of EOF velocity in a PE-grafted nanochannel is compared with that in a rigid one. It is shown that larger EOF velocity and volume flow rate are found for a PE-grafted nanochannel. In addition, AC EOF velocity is further investigated. The oscillation of velocity reduces and is restricted within the region near the PEL-electrolyte interface for higher oscillating Reynolds number Re. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhancing gelation ability of a dendritic gelator through complexation with a polyelectrolyte.

PubMed

Zhang, Zijian; Yang, Miao; Zhang, Xinjun; Zhang, Lichu; Liu, Bo; Zheng, Ping; Wang, Wei

2009-01-01

A poly(urethane amide) (PUA) dendron with long alkyl chains on its periphery was synthesized and then attached to the backbone of a polyelectrolyte, in which each unit contained a positive charge, by ionizing the carboxyl groups on the apexes of the dendrons to form a dendronized polymer. We found that both the PUA dendron and the dendronized polymer could form organogels in toluene. Interestingly, both the minimum gelation concentration and the gelation time of the dendronized polymer gelator were greatly reduced compared with the dendron alone. Our investigations showed that in the gel phase the intermolecular hydrogen bonding between adjacent dendrons creates similar supramolecular structures in both the dendron and the dendronized polymer gelator, which immobilize solvent molecules by means of interactions between dendrons and solvent molecules. Further studies on the gelation kinetics indicated that the polyelectrolyte backbone plays an important role in prearranging the attached dendritic gelators orderly and quickly into the supramolecular structures through a nucleation-elongation mechanism. Therefore, the gel-forming ability of the dendritic PUA gelator is enhanced by being complexed with the polyelectrolyte. In this work, this positive macromolecular effect is discussed in detail.

Polyelectrolyte-Functionalized Nanofiber Mats Control the Collection and Inactivation of Escherichia coli

PubMed Central

Rieger, Katrina A.; Porter, Michael; Schiffman, Jessica D.

2016-01-01

Quantifying the effect that nanofiber mat chemistry and hydrophilicity have on microorganism collection and inactivation is critical in biomedical applications. In this study, the collection and inactivation of Escherichia coli K12 was examined using cellulose nanofiber mats that were surface-functionalized using three polyelectrolytes: poly (acrylic acid) (PAA), chitosan (CS), and polydiallyldimethylammonium chloride (pDADMAC). The polyelectrolyte functionalized nanofiber mats retained the cylindrical morphology and average fiber diameter (~0.84 µm) of the underlying cellulose nanofibers. X-ray photoelectron spectroscopy (XPS) and contact angle measurements confirmed the presence of polycations or polyanions on the surface of the nanofiber mats. Both the control cellulose and pDADMAC-functionalized nanofiber mats exhibited a high collection of E. coli K12, which suggests that mat hydrophilicity may play a larger role than surface charge on cell collection. While the minimum concentration of polycations needed to inhibit E. coli K12 was 800 µg/mL for both CS and pDADMAC, once immobilized, pDADMAC-functionalized nanofiber mats exhibited a higher inactivation of E. coli K12, (~97%). Here, we demonstrate that the collection and inactivation of microorganisms by electrospun cellulose nanofiber mats can be tailored through a facile polyelectrolyte functionalization process. PMID:28773422

Counterion-Release Entropy Governs the Inhibition of Serum Proteins by Polyelectrolyte Drugs.

PubMed

Xu, Xiao; Ran, Qidi; Dey, Pradip; Nikam, Rohit; Haag, Rainer; Ballauff, Matthias; Dzubiella, Joachim

2018-02-12

Dendritic polyelectrolytes constitute high potential drugs and carrier systems for biomedical purposes. Still, their biomolecular interaction modes, in particular those determining the binding affinity to proteins, have not been rationalized. We study the interaction of the drug candidate dendritic polyglycerol sulfate (dPGS) with serum proteins using isothermal titration calorimetry (ITC) interpreted and complemented with molecular computer simulations. Lysozyme is first studied as a well-defined model protein to verify theoretical concepts, which are then applied to the important cell adhesion protein family of selectins. We demonstrate that the driving force of the strong complexation, leading to a distinct protein corona, originates mainly from the release of only a few condensed counterions from the dPGS upon binding. The binding constant shows a surprisingly weak dependence on dPGS size (and bare charge) which can be understood by colloidal charge-renormalization effects and by the fact that the magnitude of the dominating counterion-release mechanism almost exclusively depends on the interfacial charge structure of the protein-specific binding patch. Our findings explain the high selectivity of P- and L-selectins over E-selectin for dPGS to act as a highly anti-inflammatory drug. The entire analysis demonstrates that the interaction of proteins with charged polymeric drugs can be predicted by simulations with unprecedented accuracy. Thus, our results open new perspectives for the rational design of charged polymeric drugs and carrier systems.

Conjugated ionomers for photovoltaic applications: electric field driven charge separation in organic photovoltaics. Final Technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lonergan, Mark

Final technical report for Conjugated ionomers for photovoltaic applications, electric field driven charge separation in organic photovoltaics. The central goal of the work we completed was been to understand the photochemical and photovoltaic properties of ionically functionalized conjugated polymers (conjugated ionomers or polyelectrolytes) and energy conversion systems based on them. We primarily studied two classes of conjugated polymer interfaces that we developed based either upon undoped conjugated polymers with an asymmetry in ionic composition (the ionic junction) or doped conjugated polymers with an asymmetry in doping type (the p-n junction). The materials used for these studies have primarily been themore » polyacetylene ionomers. We completed a detailed study of p-n junctions with systematically varying dopant density, photochemical creation of doped junctions, and experimental and theoretical work on charge transport and injection in polyacetylene ionomers. We have also completed related work on the use of conjugated ionomers as interlayers that improve the efficiency or organic photovoltaic systems and studied several important aspects of the chemistry of ionically functionalized semiconductors, including mechanisms of so-called "anion-doping", the formation of charge transfer complexes with oxygen, and the synthesis of new polyfluorene polyelectrolytes. We also worked worked with the Haley group at the University of Oregon on new indenofluorene-based organic acceptors.« less

Adsorption of nonuniformly charged fullerene-like nanoparticles on planar polyelectrolyte brushes in aqueous solutions.

PubMed

Hu, Yiyu; Cao, Dapeng

2009-05-05

On the basis of the coarse grained model, we investigated the adsorption of nonuniformly charged fullerene-like nanoparticles on planar polyelectrolyte brushes (PEBs) in aqueous solution by using Brownian dynamics simulation. It is found that the electroneutral nanoparticles can be adsorbed by the PEB, which is attributed to the asymmetrical electrostatic interactions of the PEB with the positively charged sites and negatively charged sites of the fullerene-like nanoparticles. The simulation results indicated that the adsorption amount exhibits non-monotonic behavior with the dipole moment of nanoparticles. First, the adsorption amount increases with the dipole moment and then reaches the maximum at the dipole moment of micro = 10.45. Finally, the adsorption falls at the dipole moment of micro = 14.39. The reason may be that, at the extremely large dipole moment of micro = 14.39, the fullerene-like nanoparticles aggregate together to form a big cluster in the bulk phase, which can be confirmed by the extremely high peak in the radial distribution function between nanoparticles. Accordingly, it is difficult for nanoparticles to enter into the PEB at the dipole moment of micro = 14.39. In addition, it is also found that the brush grafting density is an important factor affecting the brush thickness.

Adsorption of reovirus by minerals and soils.

PubMed Central

Moore, R S; Taylor, D H; Reddy, M M; Sturman, L S

1982-01-01

Adsorption of [35S]methionine-labeled reovirus by 30 dry soils, minerals, and finely ground rocks suspended in synthetic freshwater at pH 7 was investigated to determine the conditions necessary for optimum virus removal during land application of wastewaters. All of the minerals and soils studied were excellent adsorbents of reovirus, with greater than 99% of the virus adsorbed after 1 h at 4 degrees C. Thereafter, virus remaining in suspension was significantly inactivated, and within 24 h a three to five log10 reduction in titer occurred. The presence of divalent cations, i.e., Ca2+ and Mg2+, in synthetic freshwater enhanced removal, whereas soluble organic matter decreased the amount of virus adsorbed in secondary effluent. The amount of virus adsorbed by these substrates was inversely correlated with the amount of organic matter, capacity to adsorb cationic polyelectrolyte, and electrophoretic mobility. Adsorption increased with increasing available surface area, as suspended infectivity was reduced further by the more finely divided substrates. However, the organic content of the soils reduced the level of infectious virus adsorbed below that expected from surface area measurements alone. The inverse correlation between virus adsorption and substrate capacity for cationic polyelectrolyte indicates that the adsorption of infectious reovirus particles is predominately a charged colloidal particle-charged surface interaction. Thus, adsorption of polyelectrolyte may be useful in predicting the fate of viruses during land application of sewage effluents and sludges. PMID:7149717

Molecular interactions in self-assembled nano-structures of chitosan-sodium alginate based polyelectrolyte complexes.

PubMed

Wasupalli, Geeta Kumari; Verma, Devendra

2018-03-16

We report here the self-assembled structures of polyelectrolyte complexes (PECs) of polyanionic sodium alginate with the polycationic chitosan at room temperature. The PECs prepared at different pH values exhibited two distinct morphologies. The chitosan-alginate PECs self-assembled into the fibrous structure in a low pH range of pH3 to 7. The PECs obtained at high pH series around pH8 and above resulted in the formation of colloidal nanoparticles in the range of 120±9.48nm to 46.02±16.66nm. The zeta potential measurement showed that PECs prepared at lower pH (pH<6) exhibited nearly neutral surface charge, whereas PECs prepared at higher pH than 6 exhibited highly negative surface charge. The molecular interactions in nano-colloids and fibers were evaluated using FTIR analysis. The results attest that the ionic state of the chitosan and alginate plays an important role controlling the morphologies of the PECS. The present study has identified the enormous potential of the polyelectrolytes complexes to exploit shape by the alteration of ionic strength. These findings might be useful in the development of novel biomaterial. The produced fibers and nanocolloids could be applied as a biomaterial for tissue engineering and drug delivery. Copyright © 2017. Published by Elsevier B.V.

Matrix polyelectrolyte capsules based on polysaccharide/MnCO₃ hybrid microparticle templates.

PubMed

Wei, Qingrong; Ai, Hua; Gu, Zhongwei

2011-06-15

An efficient strategy for biomacromolecule encapsulation based on spontaneous deposition into polysaccharide matrix-containing capsules is introduced in this study. First, hybrid microparticles composed of manganese carbonate and ionic polysaccharides including sodium hyaluronate (HA), sodium alginate (SA) and dextran sulfate sodium (DS) with narrow size distribution were synthesized to provide monodisperse templates. Incorporation of polysaccharide into the hybrid templates was successful as verified by thermogravimetric analysis (TGA) and confocal laser scanning microscopy (CLSM). Matrix polyelectrolyte microcapsules were fabricated through layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolytes (PEs) onto the hybrid particles, followed by removal of the inorganic part of the cores, leaving polysaccharide matrix inside the capsules. The loading and release properties of the matrix microcapsules were investigated using myoglobin as a model biomacromolecule. Compared to matrix-free capsules, the matrix capsules had a much higher loading capacity up to four times; the driving force is mostly due to electrostatic interactions between myoglobin and the polysaccharide matrix. From our observations, for the same kind of polysaccharide, a higher amount of polysaccharide inside the capsules usually led to better loading capacity. The release behavior of the loaded myoglobin could be readily controlled by altering the environmental pH. These matrix microcapsules may be used as efficient delivery systems for various charged water-soluble macromolecules with applications in biomedical fields. Copyright © 2010 Elsevier B.V. All rights reserved.

Layer-by-layer buildup of polysaccharide-containing films: Physico-chemical properties and mesenchymal stem cells adhesion.

PubMed

Kulikouskaya, Viktoryia I; Pinchuk, Sergei V; Hileuskaya, Kseniya S; Kraskouski, Aliaksandr N; Vasilevich, Irina B; Matievski, Kirill A; Agabekov, Vladimir E; Volotovski, Igor D

2018-03-22

Layer-by-Layer assembled polyelectrolyte films offer the opportunity to control cell attachment and behavior on solid surfaces. In the present study, multilayer films based on negatively charged biopolymers (pectin, dextran sulfate, carboxymethylcellulose) and positively charged polysaccharide chitosan or synthetic polyelectrolyte polyethyleneimine has been prepared and evaluated. Physico-chemical properties of the formed multilayer films, including their growth, morphology, wettability, stability, and mechanical properties, have been studied. We demonstrated that chitosan-containing films are characterized by the linear growth, the defect-free surface, and predominantly viscoelastic properties. When chitosan is substituted for the polyethyleneimine in the multilayer system, the properties of the formed films are significantly altered: the rigidity and surface roughness increases, the film growth acquires the exponential character. The multilayer films were subsequently used for culturing mesenchymal stem cells. It has been determined that stem cells effectively adhered to chitosan-containing films and formed on them the monolayer culture of fibroblast-like cells with high viability. Our results show that cell attachment is a complex process which is not only governed by the surface functionality because one of the key parameter effects on cell adhesion is the stiffness of polyelectrolyte multilayer films. We therefore propose our Layer-by-Layer films for applications in tissue engineering. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2018. © 2018 Wiley Periodicals, Inc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Selin, Victor; Ankner, John F.; Sukhishvili, Svetlana A.

Here in this paper, we report on the role of molecular diffusivity in the formation of nonlinearly growing polyelectrolyte multilayers (nlPEMs). Electrostatically bound polyelectrolyte multilayers were assembled from poly(methacrylic acid) (PMAA) as a polyanion and quaternized poly(2-(dimethylamino)ethyl methacrylate) (QPC) as a polycation. Film growth as measured by ellipsometry was strongly dependent on the time allowed for each polymer deposition step, suggesting that the diffusivities of the components are crucial in controlling the rate of film growth. Uptake of polyelectrolytes within nlPEMs was relatively slow and occurred on time scales ranging from minutes to hours, depending on the film thickness. Spectroscopicmore » ellipsometry measurements with nlPEM films exposed to aqueous solutions exhibited high (severalfold) degrees of film swelling and different swelling values for films exposed to QPC or PMAA solutions. FTIR spectroscopy showed that the average ionization of film-assembled PMAA increased upon binding of QPC and decreased upon binding of PMAA, in agreement with the charge regulation mechanism for weak polyelectrolytes. The use of neutron reflectometry (NR) enabled quantification of chain intermixing within the film, which was drastically enhanced when longer times were allowed for polyelectrolyte deposition. Diffusion coefficients of the polycation derived from the uptake rates of deuterated chains within hydrogenated films were of the order of 10 –14 cm 2/s, i.e., 5–6 orders of magnitude smaller than those found for diffusion of free polymer chains in solution. Exchange of the polymer solutions to buffer inhibited film intermixing. Taken together, these results contribute to understanding the mechanism of the growth of nonlinear polyelectrolyte multilayers and demonstrate the possibility of controlling film intermixing, which is highly desirable for potential future applications.« less

Poly(l-glutamic acid)-g-poly(ethylene glycol) external layer in polyelectrolyte multilayer films: Characterization and resistance to serum protein adsorption.

PubMed

Szczepanowicz, Krzysztof; Kruk, Tomasz; Świątek, Wiktoria; Bouzga, Aud M; Simon, Christian R; Warszyński, Piotr

2018-06-01

Formation of protein-resistant surfaces is a major challenge in the design of novel biomaterials and an important strategy to prevent protein adsorption is the formation of protein-resistant coatings. It can be achieved by proper modification of surfaces, e.g., by immobilization of hydrophilic polymers such as poly(ethylene glycol) (PEG). An appropriate method to immobilize PEG at charged surfaces is the adsorption of copolymers with PEG chains grafted onto polyelectrolyte backbone. The growing interest in the use of polyelectrolyte multilayer coatings in biomedical applications to improve biocompatibility and/or to prepare coating with antiadhesive properties has been the main reason for these studies. Therefore the aim was to produce protein resistant polyelectrolyte multilayer films. They were formed via the layer-by-layer approach, while their pegylation by the deposition of pegylated polyanion, PGA-g-PEG, as an external layer. The influence of PEG chain length and grafting density of PGA-g-PEG copolymers on the protein antiadhesive properties of pegylated polyelectrolyte multilayer films was investigated. To monitor the formation of pegylated and non-pegylated multilayer films, adsorption of the following proteins: HSA, Fibrinogen, and FBS were measured by quartz crystal microbalance (QCM - D). We found that protein adsorption onto all pegylated polyelectrolyte multilayers was significantly reduced in comparison to non-pegylated ones. Long-term performance tests confirmed the stability and the durability of the protein resistant properties of the pegylated multilayers. Antiadhesive properties of tested surfaces pegylated by PGA-g-PEG were compared to the available data for pegylated polycation PLL-g-PEG. Copyright © 2018 Elsevier B.V. All rights reserved.

Structure of flexible and semiflexible polyelectrolyte chains in confined spaces of slit micro/nanochannels.

PubMed

Jeon, Jonggu; Chun, Myung-Suk

2007-04-21

Understanding the behavior of a polyelectrolyte in confined spaces has direct relevance in design and manipulation of microfluidic devices, as well as transport in living organisms. In this paper, a coarse-grained model of anionic semiflexible polyelectrolyte is applied, and its structure and dynamics are fully examined with Brownian dynamics (BD) simulations both in bulk solution and under confinement between two negatively charged parallel plates. The modeling is based on the nonlinear bead-spring discretization of a continuous chain with additional long-range electrostatic, Lennard-Jones, and hydrodynamic interactions between pairs of beads. The authors also consider the steric and electrostatic interactions between the bead and the confining wall. Relevant model parameters are determined from experimental rheology data on the anionic polysaccharide xanthan reported previously. For comparison, both flexible and semiflexible models are developed accompanying zero and finite intrinsic persistence lengths, respectively. The conformational changes of the polyelectrolyte chain induced by confinements and their dependence on the screening effect of the electrolyte solution are faithfully characterized with BD simulations. Depending on the intrinsic rigidity and the medium ionic strength, the polyelectrolyte can be classified as flexible, semiflexible, or rigid. Confined flexible and semiflexible chains exhibit a nonmonotonic variation in size, as measured by the radius of gyration and end-to-end distance, with changing slit width. For the semiflexible chain, this is coupled to the variations in long-range bond vector correlation. The rigid chain, realized at low ionic strength, does not have minima in size but exhibits a sigmoidal transition. The size of confined semiflexible and rigid polyelectrolytes can be well described by the wormlike chain model once the electrostatic effects are taken into account by the persistence length measured at long length scale.

Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling

DOE PAGES

Selin, Victor; Ankner, John F.; Sukhishvili, Svetlana A.

2017-08-09

Here in this paper, we report on the role of molecular diffusivity in the formation of nonlinearly growing polyelectrolyte multilayers (nlPEMs). Electrostatically bound polyelectrolyte multilayers were assembled from poly(methacrylic acid) (PMAA) as a polyanion and quaternized poly(2-(dimethylamino)ethyl methacrylate) (QPC) as a polycation. Film growth as measured by ellipsometry was strongly dependent on the time allowed for each polymer deposition step, suggesting that the diffusivities of the components are crucial in controlling the rate of film growth. Uptake of polyelectrolytes within nlPEMs was relatively slow and occurred on time scales ranging from minutes to hours, depending on the film thickness. Spectroscopicmore » ellipsometry measurements with nlPEM films exposed to aqueous solutions exhibited high (severalfold) degrees of film swelling and different swelling values for films exposed to QPC or PMAA solutions. FTIR spectroscopy showed that the average ionization of film-assembled PMAA increased upon binding of QPC and decreased upon binding of PMAA, in agreement with the charge regulation mechanism for weak polyelectrolytes. The use of neutron reflectometry (NR) enabled quantification of chain intermixing within the film, which was drastically enhanced when longer times were allowed for polyelectrolyte deposition. Diffusion coefficients of the polycation derived from the uptake rates of deuterated chains within hydrogenated films were of the order of 10 –14 cm 2/s, i.e., 5–6 orders of magnitude smaller than those found for diffusion of free polymer chains in solution. Exchange of the polymer solutions to buffer inhibited film intermixing. Taken together, these results contribute to understanding the mechanism of the growth of nonlinear polyelectrolyte multilayers and demonstrate the possibility of controlling film intermixing, which is highly desirable for potential future applications.« less

Self-assembly of polyelectrolyte surfactant complexes using large scale MD simulation

NASA Astrophysics Data System (ADS)

Goswami, Monojoy; Sumpter, Bobby

2014-03-01

Polyelectrolytes (PE) and surfactants are known to form interesting structures with varied properties in aqueous solutions. The morphological details of the PE-surfactant complexes depend on a combination of polymer backbone, electrostatic interactions and hydrophobic interactions. We study the self-assembly of cationic PE and anionic surfactants complexes in dilute condition. The importance of such complexes of PE with oppositely charged surfactants can be found in biological systems, such as immobilization of enzymes in polyelectrolyte complexes or nonspecific association of DNA with protein. Many useful properties of PE surfactant complexes come from the highly ordered structures of surfactant self-assembly inside the PE aggregate which has applications in industry. We do large scale molecular dynamics simulation using LAMMPS to understand the structure and dynamics of PE-surfactant systems. Our investigation shows highly ordered pearl-necklace structures that have been observed experimentally in biological systems. We investigate many different properties of PE-surfactant complexation for different parameter ranges that are useful for pharmaceutical, engineering and biological applications.

Molecular understanding of polyelectrolyte binders that actively regulate ion transport in sulfur cathodes

DOE PAGES

Li, Longjun; Pascal, Tod A.; Connell, Justin G.; ...

2017-12-22

Polymer binders in battery electrodes may be either active or passive. This distinction depends on whether the polymer influences charge or mass transport in the electrode. Though it is desirable to understand how to tailor the macromolecular design of a polymer to play a passive or active role, design rules are still lacking, as is a framework to assess the divergence in such behaviors. We reveal the molecular-level underpinnings that distinguish an active polyelectrolyte binder designed for lithium-sulfur batteries from a passive alternative. The binder, a cationic polyelectrolyte, is shown to both facilitate lithium-ion transport through its reconfigurable network ofmore » mobile anions and restrict polysulfide diffusion from mesoporous carbon hosts by anion metathesis, which we show is selective for higher oligomers. These attributes then allow cells to be operated for > 100 cycles with excellent rate capability using cathodes with areal sulfur loadings up to 8.1 mg cm -2 .« less

Controlling the Growth of Staphylococcus epidermidis by Layer-By-Layer Encapsulation.

PubMed

Jonas, Alain M; Glinel, Karine; Behrens, Adam; Anselmo, Aaron C; Langer, Robert S; Jaklenec, Ana

2018-05-16

Commensal skin bacteria such as Staphylococcus epidermidis are currently being considered as possible components in skin-care and skin-health products. However, considering the potentially adverse effects of commensal skin bacteria if left free to proliferate, it is crucial to develop methodologies that are capable of maintaining bacteria viability while controlling their proliferation. Here, we encapsulate S. epidermidis in shells of increasing thickness using layer-by-layer assembly, with either a pair of synthetic polyelectrolytes or a pair of oppositely charged polysaccharides. We study the viability of the cells and their delay of growth depending on the composition of the shell, its thickness, the charge of the last deposited layer, and the degree of aggregation of the bacteria which is varied using different coating procedures-among which is a new scalable process that easily leads to large amounts of nonaggregated bacteria. We demonstrate that the growth of bacteria is not controlled by the mechanical properties of the shell but by the bacteriostatic effect of the polyelectrolyte complex, which depends on the shell thickness and charge of its outmost layer, and involves the diffusion of unpaired amine sites through the shell. The lag times of growth are sufficient to prevent proliferation for daily topical applications.

Coulombic interactions on the deposition and rotational mobility distributions of dyes in polyelectrolyte multilayer thin films.

PubMed

Li, Ye; Yip, Wai Tak

2004-12-07

We employed negatively charged fluorescein (FL), positively charged rhodamine 6G (R6G), and neutral Nile Red (NR) as molecular probes to investigate the influence of Coulombic interaction on their deposition into and rotational mobility inside polyelectrolyte multilayer (PEM) films. The entrapment efficiency of the dyes reveals that while Coulombic repulsion has little effect on dye deposition, Coulombic attraction can dramatically enhance the loading efficiency of dyes into a PEM film. By monitoring the emission polarization of single dye molecules in polyethylenimine (PEI) films, the percentages of mobile R6G, NR, and FL were determined to be 87 +/- 4%, 76 +/- 5%, and 68 +/- 3%, respectively. These mobility distributions suggest that cationic R6G enjoys the highest degree of rotational freedom, whereas anionic FL shows the least mobility because of Coulombic attraction toward cationic PEI. Regardless of charges, this high percentage of mobile molecules is in stark contrast to the 5-40% probe mobility reported from spun-cast polymer films, indicating that our PEI films contain more free volume and display richer polymer dynamics. These observations demonstrate the potential of using isolated fluorescent probes to interrogate the internal structure of a PEM film at a microscopic level.

Biocompatible Polyelectrolyte Complex Nanoparticles from Lactoferrin and Pectin as Potential Vehicles for Antioxidative Curcumin.

PubMed

Yan, Jing-Kun; Qiu, Wen-Yi; Wang, Yao-Yao; Wu, Jian-Yong

2017-07-19

Polyelectrolyte complex nanoparticles (PEC NPs) were fabricated via electrostatic interactions between positively charged heat-denatured lactoferrin (LF) particles and negatively charged pectin. The obtained PEC NPs were then utilized as curcumin carriers. PEC NPs were prepared by mixing 1.0 mg/mL solutions of heat-denatured LF and pectin at a mass ratio of 1:1 (w/w) in the absence of NaCl at pH 4.50. PEC NPs that were prepared under optimized conditions were spherical in shape with a particle size of ∼208 nm and zeta potential of ∼-32 mV. Hydrophobic curcumin was successfully encapsulated into LF/pectin PEC NPs with high encapsulation efficiency (∼85.3%) and loading content (∼13.4%). The in vitro controlled release and prominent antioxidant activities of curcumin from LF/pectin PEC NPs were observed. The present work provides a facile and fast method to synthesize nanoscale food-grade delivery systems for the improved water solubility, controlled release, and antioxidant activity of hydrophobic curcumin.

Polyelectrolyte multilayer capsules as vehicles with tunable permeability.

PubMed

Antipov, Alexei A; Sukhorukov, Gleb B

2004-11-29

This review is devoted to a novel type of polymer micro- and nanocapsules. The shell of the capsule is fabricated by alternate adsorption of oppositely charged polyelectrolytes (PEs) onto the surface of colloidal particles. Cores of different nature (organic or inorganic) with size varied from 0.1 to 10 mum can be used for templating such PE capsules. The shell thickness can be tuned in nanometer range by assembling of defined number of PE layers. The permeability of capsules depends on the pH, ionic strength, solvent, polymer composition, and shell thickness; it can be controlled and varied over wide range of substances regarding their molecular weight and charge. Including functional polymers into capsule wall, such as weak PEs or thermosensitive polymers, makes the capsule permeability sensitive to correspondent external stimuli. Permeability of the capsules is of essential interest in diverse areas related to exploitation of systems with controlled and sustained release properties. The envisaged applications of such capsules/vesicles cover biotechnology, medicine, catalysis, food industry, etc.

Polyelectrolyte-coated carbons used in the generation of blue energy from salinity differences.

PubMed

Ahualli, S; Jiménez, M L; Fernández, M M; Iglesias, G; Brogioli, D; Delgado, A V

2014-12-14

In this work we present a method for the production of clean, renewable electrical energy from the exchange of solutions with different salinities. Activated carbon films are coated with negatively or positively charged polyelectrolytes using well-established adsorption methods. When two oppositely charged coated films are placed in contact with an ionic solution, the potential difference between them will be equal to the difference between their Donnan potentials, and hence, energy can be extracted by building an electrochemical cell with such electrodes. A model is elaborated on the operation of the cell, based on the electrokinetic theory of soft particles. All the features of the model are experimentally reproduced, although a small quantitative difference concerning the maximum open-circuit voltage is found, suggesting that the coating is the key point to improve the efficiency. In the experimental conditions used, we obtain a power of 12.1 mW m(-2). Overall, the method proves to be a fruitful and simple approach to salinity-gradient energy production.

Capillary Thinning and Pinch-off Dynamics and Printability of Polyelectrolyte Solutions

NASA Astrophysics Data System (ADS)

Sharma, Vivek; Jimenez, Leidy N.; Dinic, Jelena; Parsi, Nikila

Biological macromolecules like proteins, DNA and polysaccharides, and many industrial polymers, are classified together as polyelectrolytes for in solution, the repeat units in their backbone are decorated with disassociated, charge-bearing ionic groups, surrounded by counter-ions. In diverse applications like inkjet printing, sprayable cosmetics and insecticides, paints and coatings that involve formation of fluid columns or sheets that undergo progressive thinning and pinch-off into drops, the dominant flow within the necking filament is extensional in nature. The extensional rheology response of the charged macromolecular solutions is not as well understood as that of their uncharged counterparts. Here focus on the characterization of capillary thinning and pinch-off dynamics, extensional rheology and printability of two model systems: sodium (polystyrene sulfonate) and poly(acrylic acid) by using dripping-onto-substrate (DoS) rheometry technique. Both the measured extensional relaxation times and the extensional viscosity values show salt- and polymer concentration-dependent behavior that is not expected or anticipated from the typical shear rheology response.

Polyelectrolytes tethered to a free surface

NASA Astrophysics Data System (ADS)

Dubreuil, F.; Guenoun, P.

Several attempts have been already carried out in order to tether charged chains by an end at a free fluctuating surface. We review here most of these attempts and focus on how close the physics of charged brushes can be investigated by such an approach. We first describe results about films of charged-neutral diblock copolymers spread at the surface of water. Results can be mostly rationalized in terms of charged brushes although additional structurations and fluctuations of the interface can be observed. The latter deformations are also observed when adsorbed layers of charged-neutral diblock copolymers are considered. At last, we examine how free suspended films of charged-neutral diblock copolymers can be viewed as two opposing charged brushes, both in terms of thickness and pressure.

Layer-by-Layer Polyelectrolyte Encapsulation of Mycoplasma pneumoniae for Enhanced Raman Detection

PubMed Central

Rivera-Betancourt, Omar E.; Sheppard, Edward S.; Krause, Duncan C.; Dluhy, Richard A.

2014-01-01

Mycoplasma pneumoniae is a major cause of respiratory disease in humans and accounts for as much as 20% of all community-acquired pneumonia. Existing mycoplasma diagnosis is primarily limited by the poor success rate at culturing the bacteria from clinical samples. There is a critical need to develop a new platform for mycoplasma detection that has high sensitivity, specificity, and expediency. Here we report the layer-by-layer (LBL) encapsulation of M. pneumoniae cells with Ag nanoparticles in a matrix of the polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS). We evaluated nanoparticle encapsulated mycoplasma cells as a platform for the differentiation of M. pneumoniae strains using surface enhanced Raman scattering (SERS) combined with multivariate statistical analysis. Three separate M. pneumoniae strains (M129, FH and II-3) were studied. Scanning electron microscopy and fluorescence imaging showed that the Ag nanoparticles were incorporated between the oppositely charged polyelectrolyte layers. SERS spectra showed that LBL encapsulation provides excellent spectral reproducibility. Multivariate statistical analysis of the Raman spectra differentiated the three M. pneumoniae strains with 97 – 100% specificity and sensitivity, and low (0.1 – 0.4) root mean square error. These results indicated that nanoparticle and polyelectrolyte encapsulation of M. pneumoniae is a potentially powerful platform for rapid and sensitive SERS-based bacterial identification. PMID:25017005

Pulmonary sustained release of insulin from microparticles composed of polyelectrolyte layer-by-layer assembly.

PubMed

Amancha, Kiran Prakash; Balkundi, Shantanu; Lvov, Yuri; Hussain, Alamdar

2014-05-15

The present study tests the hypothesis that layer-by-layer (LbL) nanoassembly of thin polyelectrolyte films on insulin particles provides sustained release of the drug after pulmonary delivery. LbL insulin microparticles were formulated using cationic and anionic polyelectrolytes. The microparticles were characterized for particle size, particle morphology, zeta potential and in vitro release. The pharmacokinetics and pharmacodynamics of drug were assessed by measuring serum insulin and glucose levels after intrapulmonary administration in rats. Bronchoalveolar lavage (BAL) and evans blue (EB) extravasation studies were performed to investigate the cellular or biochemical changes in the lungs caused by formulation administration. The mass median aerodynamic diameter (MMAD) of the insulin microparticles was 2.7 μm. Confocal image of the formulation particles confirmed the polyelectrolyte deposition around the insulin particles. Zeta potential measurements showed that there was charge reversal after each layering. Pulmonary administered LbL insulin formulation resulted in sustained serum insulin levels and concomitant decrease in serum glucose levels. The BAL and EB extravasation studies showed that the LbL insulin formulation did not elicit significant increase in marker enzymes activities compared to control group. These results demonstrate that the sustained release of insulin could be achieved using LbL nanoassembly around the insulin particles. Copyright © 2014 Elsevier B.V. All rights reserved.

Water-Borne Endovascular Embolics Inspired by the Undersea Adhesive of Marine Sandcastle Worms.

PubMed

Jones, Joshua P; Sima, Monika; O'Hara, Ryan G; Stewart, Russell J

2016-04-06

Transcatheter embolization is used to treat vascular malformations and defects, to control bleeding, and to selectively block blood supply to tissues. Liquid embolics are used for small vessel embolization that require distal penetration. Current liquid embolic agents have serious drawbacks, mostly centered around poor handling characteristics and toxicity. In this work, a water-borne in situ setting liquid embolic agent is described that is based on electrostatically condensed, oppositely charged polyelectrolytes-complex coacervates. At high ionic strengths, the embolic coacervates are injectable fluids that can be delivered through long narrow microcatheters. At physiological ionic strength, the embolic coacervates transition into a nonflowing solid morphology. Transcatheter embolization of rabbit renal arteries demonstrated capillary level penetration, homogeneous occlusion, and 100% devascularization of the kidney, without the embolic crossing into venous circulation. The benign water-borne composition and setting mechanism avoids many of the problems of current liquid embolics, and provides precise temporal and spatial control during endovascular embolization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Importance of pH-regulated charge density on the electrophoresis of soft particles

NASA Astrophysics Data System (ADS)

Gopmandal, Partha P.; Ohshima, H.

2017-02-01

The present study deals with the electrophoresis of spherical soft particles consisting of an ion and liquid-penetrable but liquid-flow-impenetrable inner core surrounded by an ion and fluid-penetrable polyelectrolyte layer. The inner core is considered to be dielectric and bearing basic functional group coated with polyelectrolyte layer containing acidic functional group. An approximate expression for the electrophoretic mobility of such a particle is obtained under a low potential limit. The electrophoretic behaviour of the undertaken particle is investigated for a wide range of bulk pH values and electrolyte concentrations. Our study also indicates some remarkable features of the electrophoresis e.g., occurrence of zero mobility, mobility reversal etc.

Detecting Darwinism from Molecules in the Enceladus Plumes, Jupiter's Moons, and Other Planetary Water Lagoons.

PubMed

Benner, Steven A

2017-09-01

To the astrobiologist, Enceladus offers easy access to a potential subsurface biosphere via the intermediacy of a plume of water emerging directly into space. A direct question follows: If we were to collect a sample of this plume, what in that sample, through its presence or its absence, would suggest the presence and/or absence of life in this exotic locale? This question is, of course, relevant for life detection in any aqueous lagoon that we might be able to sample. This manuscript reviews physical chemical constraints that must be met by a genetic polymer for it to support Darwinism, a process believed to be required for a chemical system to generate properties that we value in biology. We propose that the most important of these is a repeating backbone charge; a Darwinian genetic biopolymer must be a "polyelectrolyte." Relevant to mission design, such biopolymers are especially easy to recover and concentrate from aqueous mixtures for detection, simply by washing the aqueous mixtures across a polycharged support. Several device architectures are described to ensure that, once captured, the biopolymer meets two other requirements for Darwinism, homochirality and a small building block "alphabet." This approach is compared and contrasted with alternative biomolecule detection approaches that seek homochirality and constrained alphabets in non-encoded biopolymers. This discussion is set within a model for the history of the terran biosphere, identifying points in that natural history where these alternative approaches would have failed to detect terran life. Key Words: Enceladus-Life detection-Europa-Icy moon-Biosignatures-Polyelectrolyte theory of the gene. Astrobiology 17, 840-851.

Adsorbed poly(aspartate) coating limits the adverse effects of dissolved groundwater solutes on Fe0 nanoparticle reactivity with trichloroethylene.

PubMed

Phenrat, Tanapon; Schoenfelder, Daniel; Kirschling, Teresa L; Tilton, Robert D; Lowry, Gregory V

2018-03-01

For in situ groundwater remediation, polyelectrolyte-modified nanoscale zerovalent iron particles (NZVIs) have to be delivered into the subsurface, where they degrade pollutants such as trichloroethylene (TCE). The effect of groundwater organic and ionic solutes on TCE dechlorination using polyelectrolyte-modified NZVIs is unexplored, but is required for an effective remediation design. This study evaluates the TCE dechlorination rate and reaction by-products using poly(aspartate) (PAP)-modified and bare NZVIs in groundwater samples from actual TCE-contaminated sites in Florida, South Carolina, and Michigan. The effects of groundwater solutes on short- and intermediate-term dechlorination rates were evaluated. An adsorbed PAP layer on the NZVIs appeared to limit the adverse effect of groundwater solutes on the TCE dechlorination rate in the first TCE dechlorination cycle (short-term effect). Presumably, the pre-adsorption of PAP "trains" and the Donnan potential in the adsorbed PAP layer prevented groundwater solutes from further blocking NZVI reactive sites, which appeared to substantially decrease the TCE dechlorination rate of bare NZVIs. In the second and third TCE dechlorination cycles (intermediate-term effect), TCE dechlorination rates using PAP-modified NZVIs increased substantially (~100 and 200%, respectively, from the rate of the first spike). The desorption of PAP from the surface of NZVIs over time due to salt-induced desorption is hypothesized to restore NZVI reactivity with TCE. This study suggests that NZVI surface modification with small, charged macromolecules, such as PAP, helps to restore NZVI reactivity due to gradual PAP desorption in groundwater.

Particles decorated by an ionizable thermoresponsive polymer brush in water: experiments and self-consistent field modeling.

PubMed

Alves, S P C; Pinheiro, J P; Farinha, J P S; Leermakers, F A M

2014-03-20

We have synthesized anionic multistimuli responsive core-shell polymer nanoparticles with low size dispersity composed of glassy poly(methyl methacrylate) (PMMA) cores of ca. 40 nm radius and poly(N-isopropylacrylamide) (PNIPAM) anionic brush-like shells with methacrylic acid comonomers. Using dynamic light scattering, we observed a volume phase transition upon an increase in temperature and this response was pH and ionic strength dependent. Already at room temperature we observed a pronounced polyelectrolyte effect, that is, a shift of the apparent pKa extracted from the degree of dissociation of the acids as a function of the pH. The multiresponsive behavior of the hydrophobic polyelectrolyte brush has been modeled using the Scheutjens-Fleer self-consistent field (SF-SCF) approach. Using a phenomenological relation between the Flory-Huggins χ parameter and the temperature, we confront the predicted change in the brush height with the observed change of the hydrodynamic radius and degree of dissociation and obtain estimates for the average chain lengths (number of Kuhn segments) of the corona chains, the grafting density and charge density distributions. The theory reveals a rich internal structure of the hydrophobic polyelectrolyte brush, especially near the collapse transition, where we find a microphase segregated structure. Considering this complexity, it is fair to state that the theoretical predictions follow the experimental data semiquantitatively, and it is attractive to attribute the observed disparity between theory and experiments to the unknown polydispersity of the chains, the unknown distribution of the charges, or other experimental complications. More likely, however, the deviations point to significant problems of the mean field theory, which focuses solely on the radial distributions and ignores the possibility of the formation of lateral (local) inhomogeneities in partially collapsed polyelectrolyte brushes. We argue that the PNIPAM brush at room temperature is already behaving nonideally.

Resilient self-assembling hydrogels from block copolypeptide amphiphiles

NASA Astrophysics Data System (ADS)

Nowak, Andrew Paul

The ability to produce well defined synthetic polypeptides has been greatly improved by the discovery of transition metal species that mediate the controlled polymerization of N-carboxyanhydrides (NCAs). These metal species create a living polymerization system by producing control over chain length, low polydispersities, and the ability to form complex block architectures. We have applied this system to the synthesis of block copolypeptide amphiphiles. Initial block copolymers synthesized were composed of hydrophilic, cationic poly(L-Lysine) combined with hydrophobic, alpha-helical poly(L-Leucine). These Lysine- block-Leucine copolypeptides were found to form stiff, clear hydrogels at low concentration (˜1 wt%) in low ionic strength water. Based on this unexpected result we used the flexibility of our transition metal polymerization chemistry to better understand the nature and mechanisms of gel formation in these materials. Systematic changes to the original Lysine-block-Leucine copolypeptides were made by altering overall chain size, relative block length, polyelectrolyte charge, and hydrophobic secondary structure. Rheological characterization revealed that the strength of these hydrogels was primarily dependent on degree of polymerization, relative block length, and a well ordered secondary structure in the hydrophobic segment. The Lysine-block-Leucine hydrogels were formed by direct addition of water to dry polypeptide material which swelled to homogeneously fill the entire volume of liquid with no special processing. CryoTEM showed a percolating cellular network at ˜100nm that appears to be comprised of both membranes and fibers. Larger length scales studied with Laser Scanning Confocal Microscopy revealed a spontaneously formed microporous network with large (˜10mum) water rich voids. These hydrogels also displayed interesting mechanical properties including rapid recovery of solid like behavior after being sheared to a liquid and mechanical stability with increased temperature (˜90°C). The behavior of the Lysine- block-Leucine system with salt was also thoroughly investigated. With proper tuning of the relative block composition it was found that hydrogels could be optimized to possess good solubility and mechanical strength in many useful ionic solutions (˜100--200mM) such as pH buffers and cell culture media.

Statistical field theory description of inhomogeneous polarizable soft matter

NASA Astrophysics Data System (ADS)

Martin, Jonathan M.; Li, Wei; Delaney, Kris T.; Fredrickson, Glenn H.

2016-10-01

We present a new molecularly informed statistical field theory model of inhomogeneous polarizable soft matter. The model is based on fluid elements, referred to as beads, that can carry a net monopole of charge at their center of mass and a fixed or induced dipole through a Drude-type distributed charge approach. The beads are thus polarizable and naturally manifest attractive van der Waals interactions. Beyond electrostatic interactions, beads can be given soft repulsions to sustain fluid phases at arbitrary densities. Beads of different types can be mixed or linked into polymers with arbitrary chain models and sequences of charged and uncharged beads. By such an approach, it is possible to construct models suitable for describing a vast range of soft-matter systems including electrolyte and polyelectrolyte solutions, ionic liquids, polymerized ionic liquids, polymer blends, ionomers, and block copolymers, among others. These bead models can be constructed in virtually any ensemble and converted to complex-valued statistical field theories by Hubbard-Stratonovich transforms. One of the fields entering the resulting theories is a fluctuating electrostatic potential; other fields are necessary to decouple non-electrostatic interactions. We elucidate the structure of these field theories, their consistency with macroscopic electrostatic theory in the absence and presence of external electric fields, and the way in which they embed van der Waals interactions and non-uniform dielectric properties. Their suitability as a framework for computational studies of heterogeneous soft matter systems using field-theoretic simulation techniques is discussed.

Viral genome structures, charge, and sequences are optimal for capsid assembly

NASA Astrophysics Data System (ADS)

Hagan, Michael

2014-03-01

For many viruses, the spontaneous assembly of a capsid shell around the nu-cleic acid (NA) genome is an essential step in the viral life cycle. Capsid formation is a multicomponent, out-of-equilibrium assembly process for which kinetic effects and thermodynamic constraints compete to determine the outcome. Understand-ing how viral components drive highly efficient assembly under these constraints could promote biomedical efforts to block viral propagation, and would elucidate the factors controlling assembly in a wide range of systems containing proteins and polyelectrolytes. This talk will describe coarse-grained models of capsid proteins and NAs with which we investigate the dynamics and thermodynamics of virus assembly. In con-trast to recent theoretical models, we find that capsids spontaneously `overcharge' that is, the NA length which is kinetically and thermodynamically optimal possess-es a negative charge greater than the positive charge of the capsid. When applied to specific virus capsids, the calculated optimal NA lengths closely correspond to the natural viral genome lengths. These results suggest that the features included in this model (i.e. electrostatics, excluded volume, and NA tertiary structure) play key roles in determining assembly thermodynamics and consequently exert selec-tive pressure on viral evolution. I will then discuss mechanisms by which se-quence-specific interactions between NAs and capsid proteins promote selective encapsidation of the viral genome. This work was supported by NIH R01GM108021 and the Brandeis MRSEC NSF-MRSEC-0820492.

Statistical field theory description of inhomogeneous polarizable soft matter.

PubMed

Martin, Jonathan M; Li, Wei; Delaney, Kris T; Fredrickson, Glenn H

2016-10-21

We present a new molecularly informed statistical field theory model of inhomogeneous polarizable soft matter. The model is based on fluid elements, referred to as beads, that can carry a net monopole of charge at their center of mass and a fixed or induced dipole through a Drude-type distributed charge approach. The beads are thus polarizable and naturally manifest attractive van der Waals interactions. Beyond electrostatic interactions, beads can be given soft repulsions to sustain fluid phases at arbitrary densities. Beads of different types can be mixed or linked into polymers with arbitrary chain models and sequences of charged and uncharged beads. By such an approach, it is possible to construct models suitable for describing a vast range of soft-matter systems including electrolyte and polyelectrolyte solutions, ionic liquids, polymerized ionic liquids, polymer blends, ionomers, and block copolymers, among others. These bead models can be constructed in virtually any ensemble and converted to complex-valued statistical field theories by Hubbard-Stratonovich transforms. One of the fields entering the resulting theories is a fluctuating electrostatic potential; other fields are necessary to decouple non-electrostatic interactions. We elucidate the structure of these field theories, their consistency with macroscopic electrostatic theory in the absence and presence of external electric fields, and the way in which they embed van der Waals interactions and non-uniform dielectric properties. Their suitability as a framework for computational studies of heterogeneous soft matter systems using field-theoretic simulation techniques is discussed.

Polyplex formation between four-arm poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) and plasmid DNA in gene delivery.

PubMed

He, E; Yue, C Y; Simeon, F; Zhou, L H; Too, H P; Tam, K C

2009-12-01

Amphiphilic polyelectrolytes comprising cationic and uncharged hydrophilic segments condensed negatively charged DNA to form a core-shell structure stabilized by a layer of hydrophilic corona chains. At physiological pH, four-arm star-shaped poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) (four-arm PEO-b-PDEAEMA) block copolymer possessed positively charged amine groups that interacted with negatively charged plasmid DNA to form polymer/DNA complexes. The mechanism and physicochemical properties of the complex formation were investigated at varying molar ratio of amine groups on polymer chains and phosphate group on plasmid DNA segments (N/P ratio). The capability of the star block copolymer to condense DNA was demonstrated through gel electrophoresis and ethidium bromide exclusion assay. In the absence of salt, the hydrodynamic radius of polyplexes was about 94 nm at low polymer/DNA ratio, and it decreased to about 34 nm at large N/P ratios, forming a compact spherical structure with a weighted average molecular weight of 4.39 +/- 0.22 x 10(6) g/mol. Approximately 15 polymeric chains were required to condense a plasmid DNA. The addition of monovalent salt to the polyplexes significantly altered the size of the complexes, which would have an impact on cell transfection. Because of the electrostatic interaction induced by the diffusion of small ions, the polyplex increased in size to about 53 nm with a less compact structure. In vitro cytotoxicty of polymer and polymer/pDNA complexes were evaluated, and the polyplexes exhibited low toxicity at low N/P ratios. At N/P ratio of 4.5, the four-arm PEO-b-PDEAEMA showed the highest level of transfection in Neuro-2A cells. These observations showed that the star-shaped multi-arm polymers offers interesting properties in self-association and condensation ability for plasmid DNA and can serve as a nonviral DNA delivery system. Copyright 2008 Wiley Periodicals, Inc.

Layer-by-layer polyelectrolyte coating for surface-enhanced Raman scattering on gold nanostars inside hollow core photonic crystal fibers

NASA Astrophysics Data System (ADS)

Burmistrova, Natalia A.; Bondarenko, Sergei D.; Bratashov, Daniil N.; Shuvalov, Andrei A.; Chibrova, Anastasiya A.; Khlebtsov, Boris N.; Skibina, Julia S.; Goryacheva, Irina Y.

2018-04-01

Photonic crystal fibers with hollow core (HC PCFs) are a specific class of optical fibers characterized by microstructure with periodic holes oriented along fiber. The combination of HC PCF with Raman spectroscopy for biosensors creation is attractive in the terms of the low sample volume, the possibility to increase the integration time without sample degradation and maintaining constant focus during experiments. Here we propose layer-by-layer polyelectrolyte coating of HC PCF inner surface in order to obtain charge-selective absorption of analyte, stabilization of Surface-Enhanced Raman scattering (SERS)-active gold nanoparticles. Distance between SERS hotspots and glass reduces nonlinear signals from glass, and increases signal-to-noise ratio of SERS spectra.

Surface modification of upconverting nanoparticles by layer-by-layer assembled polyelectrolytes and metal ions.

PubMed

Palo, Emilia; Salomäki, Mikko; Lastusaari, Mika

2017-12-15

Modificating and protecting the upconversion luminescence nanoparticles is important for their potential in various applications. In this work we demonstrate successful coating of the nanoparticles by a simple layer-by-layer method using negatively charged polyelectrolytes and neodymium ions. The layer fabrication conditions such as number of the bilayers, solution concentrations and selected polyelectrolytes were studied to find the most suitable conditions for the process. The bilayers were characterized and the presence of the desired components was studied and confirmed by various methods. In addition, the upconversion luminescence of the bilayered nanoparticles was studied to see the effect of the surface modification on the overall intensity. It was observed that with selected deposition concentrations the bilayer successfully shielded the particle resulting in stronger upconversion luminescence. The layer-by-layer method offers multiple possibilities to control the bilayer growth even further and thus gives promises that the use of upconverting nanoparticles in applications could become even easier with less modification steps in the future. Copyright © 2017 Elsevier Inc. All rights reserved.

Top-down and Bottom-up Approaches in Production of Aqueous Nanocolloids of Low Soluble Drug Paclitaxel

PubMed Central

Pattekari, P.; Zheng, Z.; Zhang, X.; Levchenko, T.; Torchilin, V.

2015-01-01

Nano-encapsulation of poorly soluble anticancer drug was developed with sonication assisted layer-by-layer polyelectrolyte coating (SLbL). We changed the strategy of LbL-encapsulation from making microcapsules with many layers in the walls for encasing highly soluble materials to using very thin polycation / polyanion coating on low soluble nanoparticles to provide their good colloidal stability. SLbL encapsulation of paclitaxel resulted in stable 100-200 nm diameter colloids with high electrical surface ξ-potential (of -45 mV) and drug content in the nanoparticles of 90 wt %. In the top-down approach, nanocolloids were prepared by rupturing powder of paclitaxel using ultrasonication and simultaneous sequential adsorption of oppositely charged biocompatible polyelectrolytes. In the bottom-up approach paclitaxel was dissolved in organic solvent (ethanol or acetone), and drug nucleation was initiated by gradual worsening the solution with the addition of aqueous polyelectrolyte assisted by ultrasonication. Paclitaxel release rates from such nanocapsules were controlled by assembling multilayer shells with variable thicknesses and are in the range of 10-20 hours. PMID:21442095

Layer-by-layer introduction of poly(phenylenevinylene) onto microspheres and probing the influence from the weak/strong polyanion spacer-layers.

PubMed

Song, Jing; Qiu, Tian; Chen, Yun; Zhang, Wei; Fan, Li-Juan

2015-08-15

The layer-by-layer (LBL) technique was employed for preparing fluorescent microspheres with a core-shell structure by the alternating adsorption of positively charged poly(p-phenylenevinylene) precursor (pre-PPV) and the polyanions onto polymer substrate spheres, followed by the thermal elimination to convert pre-PPV into fluorescent poly(p-phenylenevinylene) (PPV). Weak polyelectrolytes poly(acrylic acid) (PAA) (usually in a partly ionized form) and strong polyelectrolytes poly(sodium-p-styrenesulfonate) (PSS) were used as the anions to space the PPV layers and reduce the fluorescence self-quenching. Flow cytometry, combined with spectroscopy and microscopy, were used to study the structure and photophysical properties of the resulting microspheres. Optimization of the processing factors was carried out. PAA and PSS as weak and strong polyelectrolytes, respectively, displayed very different influence on the final emission of the spheres. Such difference was attributed to different inherent characteristics of PAA and PSS after detailed investigation in many aspects. In addition, the fluorescent spheres were found to have excellent photostability and thermal stability. Copyright © 2015 Elsevier Inc. All rights reserved.

Evidence of a two-step process and pathway dependency in the thermodynamics of poly(diallyldimethylammonium chloride)/poly(sodium acrylate) complexation.

PubMed

Vitorazi, L; Ould-Moussa, N; Sekar, S; Fresnais, J; Loh, W; Chapel, J-P; Berret, J-F

2014-12-21

Recent studies have pointed out the importance of polyelectrolyte assembly in the elaboration of innovative nanomaterials. Beyond their structures, many important questions on the thermodynamics of association remain unanswered. Here, we investigate the complexation between poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium acrylate) (PANa) chains using a combination of three techniques: isothermal titration calorimetry (ITC), static and dynamic light scattering and electrophoresis. Upon addition of PDADMAC to PANa or vice-versa, the results obtained by the different techniques agree well with each other, and reveal a two-step process. The primary process is the formation of highly charged polyelectrolyte complexes of size 100 nm. The secondary process is the transition towards a coacervate phase made of rich and poor polymer droplets. The binding isotherms measured are accounted for using a phenomenological model that provides the thermodynamic parameters for each reaction. Small positive enthalpies and large positive entropies consistent with a counterion release scenario are found throughout this study. Furthermore, this work stresses the importance of the underestimated formulation pathway or mixing order in polyelectrolyte complexation.

Self-assembled morphologies of an amphiphilic Y-shaped weak polyelectrolyte in a thin film.

PubMed

Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

2017-11-29

Different from the self-assembly of neutral polymers, polyelectrolytes self-assemble into smaller aggregates with a more loosely assembled structure, which results from the repulsive forces acting between similar electrical compositions with the introduction of ions. The Y-shaped weak polyelectrolytes self-assemble into a core-shell type cylindrical structure with a hexagonal arrangement in a thin film, whose thickness is smaller than the gyration radius of the polymer chain. The corresponding formation mechanism consists of enrichment of the same components, adjustment of the shape of the aggregate, and the subsequent separation into individual aggregates. With the increase in the thickness of the thin film until it exceeds the gyration radius of the polymer chain, combined with the greater freedom of movement along the direction of thin film thickness, the self-assembled structure changes into a micellar structure. Under confinement, the repulsive force to the polymeric components is weakened by the repulsive forces among polyelectrolyte components with like charges, and this helps in generating aggregates with more uniform size and density distribution. In particular, when the repulsive force between the walls and the core forming components is greater than that between the walls and the shell forming components, such asymmetric confinement produces a crossed-cylindrical structure with nearly perpendicular arrangement of two cylinder arrays. Similarly, a novel three-crossed cylinder morphology is self-assembled upon removal of confinement.

Conductive hydrogel containing 3-ionene

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor)

1977-01-01

Cationic polyelectrolytes formed by the polymerization in absence of oxygen of a monomer of the general formula: dispersed ##STR1## where x is 3 or more than 6 and Z is I, Br or Cl to form high charge density linear polymers are dispered in a water-soluble polymer such as polyvinyl alcohol to form a conductive hydrogel.

Thermodynamic characterization of the interaction behavior of a hydrophobically modified polyelectrolyte and oppositely charged surfactants in aqueous solution: effect of surfactant alkyl chain length.

PubMed

Bai, Guangyue; Nichifor, Marieta; Lopes, António; Bastos, Margarida

2005-01-13

We have used a precision isothermal titration microcalorimeter (ITC) to measure the enthalpy curves for the interaction of a hydrophobically modified polyelectrolyte (D40OCT30) with oppositely charged surfactants (SC(n)S) in aqueous solution. D40OCT30 is a newly synthesized polymer based on dextran having pendant N-(2-hydroxypropyl)-N,N-dimethyl-N-octylammonium chloride groups randomly distributed along the polymer backbone with degree of substitution of 28.1%. The employed anionic surfactants are sodium octyl sulfate (SC(8)S) and sodium tetradecyl sulfate (SC(14)S). Microcalorimetric results along with turbidity and kinematic viscosity measurements demonstrate systematically the thermodynamic characterization of the interaction of D40OCT30/SC(n)S. A three-dimensional diagram with the derived phase boundaries is drawn to describe the effect of the alkyl chain length of surfactant and of the ratio between surfactant and pendant groups on the interaction. A more complete picture of the interaction mechanism for D40OCT30/SC(n)S systems is proposed here.

Energy conversion in polyelectrolyte hydrogels

NASA Astrophysics Data System (ADS)

Olvera de La Cruz, Monica; Erbas, Aykut; Olvera de la Cruz Team

Energy conversion and storage have been an active field of research in nanotechnology parallel to recent interests towards renewable energy. Polyelectrolyte (PE) hydrogels have attracted considerable attention in this field due to their mechanical flexibility and stimuli-responsive properties. Ideally, when a hydrogel is deformed, applied mechanical work can be converted into electrostatic, elastic and steric-interaction energies. In this talk, we discuss the results of our extensive molecular dynamics simulations of PE hydrogels. We demonstrate that, on deformation, hydrogels adjust their deformed state predominantly by altering electrostatic interactions between their charged groups rather than excluded-volume and bond energies. This is due to the hydrogel's inherent tendency to preserve electro-neutrality in its interior, in combination with correlations imposed by backbone charges. Our findings are valid for a wide range of compression ratios and ionic strengths. The electrostatic-energy alterations that we observe in our MD simulations may induce pH or redox-potential changes inside the hydrogels. The resulting energetic difference can be harvested, for instance, analogously to a Carnot engine, or facilitated for sensor applications. Center for Bio-inspired Energy Science (CBES).

Molecular Origins of Thermal Transitions in Polyelectrolyte Assemblies

NASA Astrophysics Data System (ADS)

Yildirim, Erol; Zhang, Yanpu; Antila, Hanne S.; Lutkenhaus, Jodie L.; Sammalkorpi, Maria; Aalto Team; Texas A&M Team

2015-03-01

Polyelectrolyte (PE) multilayers and complexes formed from oppositely charged polymers can exhibit extraordinary superhydrophobicity, mechanical strength and responsiveness resulting in applications ranging functional membranes, optics, sensors and drug delivery. Depending on the assembly conditions, PE assemblies may undergo a thermal transition from glassy to soft behavior under heating. Our earlier work using thermal analysis measurements shows a distinct thermal transition for PE layer-by-layer (LbL) systems assembled with added salt but no analogous transition in films assembled without added salt or dry systems. These findings raise interesting questions on the nature of the thermal transition; here, we explore its molecular origins through characterization of the PE aggregates by temperature-controlled all-atom molecular dynamics simulations. We show via molecular simulations the thermal transition results from the existence of an LCST (lower critical solution temperature) in the PE systems: the diffusion behavior, hydrogen bond formation, and bridging capacity of water molecules plasticizing the complex changes at the transition temperature. We quantify the behavior, map its chemistry specificity through comparison of strongly and weakly charged PE complexes, and connect the findings to our interrelated QCM-D experiments.

Formation of charge-nanopatterned templates with flexible geometry via layer by layer deposition of polyelectrolytes for directed self-assembly of gold nanoparticles

NASA Astrophysics Data System (ADS)

Sayin, Mustafa; Dahint, Reiner

2017-03-01

Nanostructure formation via self-assembly processes offers a fast and cost-effective approach to generate surface patterns on large lateral scale. In particular, if the high precision of lithographic techniques is not required, a situation typical of many biotechnological and biomedical applications, it may be considered as the method of choice as it does not require any sophisticated instrumentation. However, in many cases the variety and complexity of the surface structures accessible with a single self-assembly based technique is limited. Here, we report on a new approach which combines two different self-assembly strategies, colloidal lithography and layer-by-layer deposition of polyelectrolytes, in order to significantly expand the spectrum of accessible patterns. In particular, flat and donut-like charge-patterned templates have been generated, which facilitate subsequent deposition of gold nanoparticles in dot, grid, ring, out-of-ring and circular patch structures. Potential applications are e.g. in the fields of biofunctional interfaces with well-defined lateral dimensions, optical devices with tuned properties, and controlled three-dimensional material growth.

Kinetics of swelling of polyelectrolyte gels: Fixed degree of ionization

NASA Astrophysics Data System (ADS)

Sen, Swati; Kundagrami, Arindam

2015-12-01

The swelling kinetics of uncharged and charged polymer (polyelectrolyte) gels in salt-free conditions is studied in one dimension by solving the constitutive equation of motion (Newton's law for the elementary gel volume) of the displacement variable by two theoretical methods: one in which the classical definition of stress is used with the bulk modulus taken as a parameter, and the other in which a phenomenological expression of the osmotic stress as a function of polymer density and degree of ionization is taken as an input to the dynamics. The time-evolution profiles for spatially varying polymer density and stress, along with the location of the gel-solvent interface, are obtained from the two methods. We show that both the polymer density (volume fraction) and stress inside the gel follow expected behaviours of being maximum for the uniformly shrunken gel, and relaxing slowly to the lowest values as the gel approaches equilibrium. We further show that, by comparing the temporal profiles of the gel-solvent interface and other variables between the two methods, one may attempt to assign an effective bulk modulus to the polyelectrolyte gel as a function of the degree of ionization and other parameters of the gel such as hydrophobicity, cross-link density, and the temperature. The major result we get is that the effective bulk modulus of a polyelectrolyte gel increases monotonically with its degree of ionization. In the process of identifying the parameters for a monotonic swelling, we calculated using a well-known expression of the free energy the equilibrium results of two-phase co-existence and the critical point of a polyelectrolyte gel with a fixed degree of ionization.

Kinetics of swelling of polyelectrolyte gels: Fixed degree of ionization.

PubMed

Sen, Swati; Kundagrami, Arindam

2015-12-14

The swelling kinetics of uncharged and charged polymer (polyelectrolyte) gels in salt-free conditions is studied in one dimension by solving the constitutive equation of motion (Newton's law for the elementary gel volume) of the displacement variable by two theoretical methods: one in which the classical definition of stress is used with the bulk modulus taken as a parameter, and the other in which a phenomenological expression of the osmotic stress as a function of polymer density and degree of ionization is taken as an input to the dynamics. The time-evolution profiles for spatially varying polymer density and stress, along with the location of the gel-solvent interface, are obtained from the two methods. We show that both the polymer density (volume fraction) and stress inside the gel follow expected behaviours of being maximum for the uniformly shrunken gel, and relaxing slowly to the lowest values as the gel approaches equilibrium. We further show that, by comparing the temporal profiles of the gel-solvent interface and other variables between the two methods, one may attempt to assign an effective bulk modulus to the polyelectrolyte gel as a function of the degree of ionization and other parameters of the gel such as hydrophobicity, cross-link density, and the temperature. The major result we get is that the effective bulk modulus of a polyelectrolyte gel increases monotonically with its degree of ionization. In the process of identifying the parameters for a monotonic swelling, we calculated using a well-known expression of the free energy the equilibrium results of two-phase co-existence and the critical point of a polyelectrolyte gel with a fixed degree of ionization.

Fabrication and physical-chemical characterisation of polyelectrolyte microparticles: platform for controlled release of bioactives.

PubMed

Sun, Yuhui; Travas-Sejdic, Jadranka; Wen, Jingyuan; Alany, Raid G

2009-08-01

Porous CaCO(3) microparticles were fabricated by colloidal crystallization. Two oppositely charged polyelectrolytes, poly (styrene sulfonate, PSS) and poly (allylamine hydrochloride, PAH) were adsorbed layer-by-layer on the CaCO(3) templates. Polyelectrolyte microcapsules were then obtained by removing the CaCO(3) core. Scanning electron microscopy (SEM), energy-dispersion X-ray analysis (EDX), laser diffraction particle sizing and Raman spectroscopy were employed to characterize the physico-chemical properties of the constructed microcapsules. In vitro drug release studies were conducted using the model water-soluble drug Rhodamine B. Factors such as the number of polyelectrolyte layers and pH were investigated. SEM micrographs revealed uniform CaCO(3) microparticles, nearly spherical in shape with pronounced surface roughness, and highly developed interior porous structure. The surface of polyelectrolyte coated particles became rougher than the initial CaCO(3) microparticles. The acquired SEM micrographs of the (PSS/PAH)(n) microcapsules indicated that the number of layers affected the morphology of the microcapsules. The (PSS/PAH)(3) microcapsules revealed a very porous network with many holes resembling the initial morphology of CaCO(3) microparticles. Raman spectra showed peaks at 1125 cm(-1) (S=O bond) and 1600 cm(-1) (aromatic ring stretching) which represented the PSS molecule. The thickness of each layer was about 10 to 20 nm and it can be tailored to such nanometer level by controlling the number of adsorbed layers. The in vitro release of Rhodamine B was dependent on both the number of wall bilayers as well as the pH of the release media. These systems provide an opportunity for the development of controlled release dosage forms with greater effectiveness in the treatment of chronic conditions.

Sampling Long- versus Short-Range Interactions Defines the Ability of Force Fields To Reproduce the Dynamics of Intrinsically Disordered Proteins.

PubMed

Mercadante, Davide; Wagner, Johannes A; Aramburu, Iker V; Lemke, Edward A; Gräter, Frauke

2017-09-12

Molecular dynamics (MD) simulations have valuably complemented experiments describing the dynamics of intrinsically disordered proteins (IDPs), particularly since the proposal of models to solve the artificial collapse of IDPs in silico. Such models suggest redefining nonbonded interactions, by either increasing water dispersion forces or adopting the Kirkwood-Buff force field. These approaches yield extended conformers that better comply with experiments, but it is unclear if they all sample the same intrachain dynamics of IDPs. We have tested this by employing MD simulations and single-molecule Förster resonance energy transfer spectroscopy to sample the dimensions of systems with different sequence compositions, namely strong and weak polyelectrolytes. For strong polyelectrolytes in which charge effects dominate, all the proposed solutions equally reproduce the expected ensemble's dimensions. For weak polyelectrolytes, at lower cutoffs, force fields abnormally alter intrachain dynamics, overestimating excluded volume over chain flexibility or reporting no difference between the dynamics of different chains. The TIP4PD water model alone can reproduce experimentally observed changes in extensions (dimensions), but not quantitatively and with only weak statistical significance. Force field limitations are reversed with increased interaction cutoffs, showing that chain dynamics are critically defined by the presence of long-range interactions. Force field analysis aside, our study provides the first insights into how long-range interactions critically define IDP dimensions and raises the question of which length range is crucial to correctly sample the overall dimensions and internal dynamics of the large group of weakly charged yet highly polar IDPs.

Detecting Darwinism from Molecules in the Enceladus Plumes, Jupiter's Moons, and Other Planetary Water Lagoons

PubMed Central

2017-01-01

Abstract To the astrobiologist, Enceladus offers easy access to a potential subsurface biosphere via the intermediacy of a plume of water emerging directly into space. A direct question follows: If we were to collect a sample of this plume, what in that sample, through its presence or its absence, would suggest the presence and/or absence of life in this exotic locale? This question is, of course, relevant for life detection in any aqueous lagoon that we might be able to sample. This manuscript reviews physical chemical constraints that must be met by a genetic polymer for it to support Darwinism, a process believed to be required for a chemical system to generate properties that we value in biology. We propose that the most important of these is a repeating backbone charge; a Darwinian genetic biopolymer must be a “polyelectrolyte.” Relevant to mission design, such biopolymers are especially easy to recover and concentrate from aqueous mixtures for detection, simply by washing the aqueous mixtures across a polycharged support. Several device architectures are described to ensure that, once captured, the biopolymer meets two other requirements for Darwinism, homochirality and a small building block “alphabet.” This approach is compared and contrasted with alternative biomolecule detection approaches that seek homochirality and constrained alphabets in non-encoded biopolymers. This discussion is set within a model for the history of the terran biosphere, identifying points in that natural history where these alternative approaches would have failed to detect terran life. Key Words: Enceladus—Life detection—Europa—Icy moon—Biosignatures—Polyelectrolyte theory of the gene. Astrobiology 17, 840–851. PMID:28665680

Ionic content and permeability of polyelectrolyte multilayers and complexes

NASA Astrophysics Data System (ADS)

Ghostine, Ramy A.

Ultrathin films of polyelectrolyte multilayers (PEMUs) are built by the alternating deposition of oppositely charged polymers from aqueous solutions onto a clean substrate. The most used protocol to fabricate this type of films is called the Layer-by-Layer assembly technique. The type of polyelectrolytes, the buildup conditions, and the post-assembly treatments can be modified in order to control both the chemical and physical properties of multilayers. In recent years, multilayers have been used in commercially available products, corrosion protection, biocompatible surfaces, hydrophobic and hydrophilic coatings and chromatographic applications. Their robustness and stability make polyelectrolyte multilayer thin films good candidates for a series of other applications such as cell growth control, ion exchange membranes, drug delivery, sensors and electronics. In this dissertation, the permeability of polyelectrolyte multilayers made from poly(diallyldimethylammonium chloride) (PDADMAC) and sodium poly(4-styrene sulfonate) (NaPSS) is discussed in details. The permeability was studied by measuring the flux of redox active ions across a PEMU coated electrode. The effect of temperature, salt type and concentration was studied and it was determined that the flux of ions increases with temperature and salt concentration, and the permeability of ions strongly depends on the type of salt ions present in solution. The membrane concentration of the redox active ion was also calculated using attenuated total reflectance Fourier transform infra red spectroscopy. In another part of this dissertation, the ionic content of PEMUs was investigated by using radioactive counterions to track the ratio of positive to negative polymer repeat units. It was found that the accepted model of charge overcompensation for each layer is incorrect. In fact, overcompensation at the surface occurs only on the addition of the polycation, whereas the polyanion merely compensates the polycation. After the assembly of about a dozen layers, positive sites begin to accrue in the multilayer. The buildup mechanism is highly asymmetric with respect to the layer number, thus a new model profile for PEMU was employed. The critical impact of asymmetric growth on various properties of multilayers is also discussed. Thickness change, surface roughness, mechanical properties and ionic content of PEMUs were also studied in another part of this dissertation. The effect of salt annealing on these properties was investigated by the use of radiolabeling technique and atomic force microscopy. It was determined that salt annealing causes the polymer mobility in the multilayer to increase, reducing the amount of extrinsic charges and decreasing the surface roughness of the multilayer. The incorporation of 2nd generation fibroblast growth factor was studied in another chapter of this dissertation. FGF-1 is an important protein used in the wound healing process. The addition of FGF into films of PEMU was successful after modifying the ionic content of these films. It was shown that treating PSS terminated PEMU films with 10 mM PSS at high salt concentration would remove all positive extrinsic charges from the multilayer and add extra PSS chains in the bulk of the film. The addition of extra PSS depends on the salt concentration used during the PSS treatment. The highest amount of incorporated FGF was 58 mug cm-2. The release of FGF in phosphate buffer saline solution was also tracked for 30 days period. A total of 13 mug cm-2 of FGF were released from (PDADMA/PSS) 10 when treated with PSS at 1.5 M NaCl. Doping constants and diffusion coefficients for an extruded, stoichiometric, dense polyelectrolyte complex, exPEC, were determined for a Hofmeister series of anions in the last part of this dissertation. Both parameters describe the extent and speed to which a complex may be doped, where they followed a Hofmeister ordering and covered a wide range of response. Doping and undoping kinetics of polyelectrolyte complexes of PDADMA and PSS were also investigated using conductivity and radioactivity techniques. Tracer diffusion of radiolabeled Na+, compared with coupled diffusion of NaCl, revealed slightly faster diffusion of Na+ compared to Cl- withing the PEC.

Simultaneous detection of refractive index and surface charges in nanolaser biosensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Keisuke; Kishi, Yoji; Hachuda, Shoji

2015-01-12

The emission intensity of a GaInAsP photonic crystal nanolaser is affected by the pH of the solution, in which the nanolaser is immersed. This phenomenon can be explained by the change in the redox potential, which modifies the filling of electrons at surface states of the semiconductor and hence the nonradiative surface recombination. This phenomenon allows the nanolaser to simultaneously and independently detect the refractive index and electric charges near the surface on the basis of the variation in emission wavelength and intensity, respectively. This paper demonstrates this function through alternate deposition of charged polyelectrolytes and hybridization of deoxyribonucleic acids.

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

PubMed

Pi, Yingying; Shang, Yazhuo; Peng, Changjun; Liu, Honglai; Hu, Ying; Jiang, Jianwen

2006-07-01

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.

Separation of charge-regulated polyelectrolytes by pH-assisted diffusiophoresis.

PubMed

Hsu, Jyh-Ping; Hsu, Yen-Rei; Shang-Hung, Hsieh; Tseng, Shiojenn

2017-03-29

The potential of separating colloidal particles through simultaneous application of a salt gradient and a pH gradient, or pH-assisted diffusiophoresis, is evaluated by considering the case of spherical polyelectrolytes (PEs) having different equilibrium dissociation constants in an aqueous solution with KCl as the background salt. The simulation results gathered reveal that the dependence of the particle velocity on pH is more sensitive than that in pH-assisted electrophoresis, where an electric field and a pH gradient are applied simultaneously. This implies that the separation efficiency of pH-assisted diffusiophoresis can be better than that of pH-assisted electrophoresis. In particular, two types of PE having different equilibrium dissociation constants can be separated effectively by applying the former by enhancing/reducing their diffusiophoretic velocities.

Electrostatic contribution to twist rigidity of DNA.

PubMed

Mohammad-Rafiee, Farshid; Golestanian, Ramin

2004-06-01

The electrostatic contribution to the twist rigidity of DNA is studied, and it is shown that the Coulomb self-energy of the double-helical sugar-phosphate backbone makes a considerable contribution-the electrostatic twist rigidity of DNA is found to be C(elec) approximately 5 nm, which makes up about 7% of its total twist rigidity ( C(DNA) approximately 75 nm). The electrostatic twist rigidity is found, however, to depend only weakly on the salt concentration, because of a competition between two different screening mechanisms: (1) Debye screening by the salt ions in the bulk, and (2) structural screening by the periodic charge distribution along the backbone of the helical polyelectrolyte. It is found that, depending on the parameters, the electrostatic contribution to the twist rigidity could stabilize or destabilize the structure of a helical polyelectrolyte.

Polyelectrolyte multilayer assembly as a function of pH and ionic strength using the polysaccharides chitosan and heparin.

PubMed

Boddohi, Soheil; Killingsworth, Christopher E; Kipper, Matt J

2008-07-01

The goal of this work is to explore the effects of solution ionic strength and pH on polyelectrolyte multilayer (PEM) assembly, using biologically derived polysaccharides as the polyelectrolytes. We used the layer-by-layer (LBL) technique to assemble PEM of the polysaccharides heparin (a strong polyanion) and chitosan (a weak polycation) and characterized the sensitivity of the PEM composition and layer thickness to changes in processing parameters. Fourier-transform surface plasmon resonance (FT-SPR) and spectroscopic ellipsometry provided in situ and ex situ measurements of the PEM thickness, respectively. Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) provided details of the chemistry (i.e., composition, electrostatic interactions) of the PEM. We found that when PEM were assembled from 0.2 M buffer, the PEM thickness could be increased from less than 2 nm per bilayer to greater than 4 nm per bilayer by changing the solution pH; higher and lower ionic strength buffer solutions resulted in narrower ranges of accessible thickness. Molar composition of the PEM was not very sensitive to solution pH or ionic strength, but pH did affect the interactions between the sulfonates in heparin and amines in chitosan when PEM were assembled from 0.2 M buffer. Changes in the PEM thickness with pH and ionic strength can be interpreted through descriptions of the charge density and conformation of the polyelectrolyte chains in solution.

'Soft' amplifier circuits based on field-effect ionic transistors.

PubMed

Boon, Niels; Olvera de la Cruz, Monica

2015-06-28

Soft materials can be used as the building blocks for electronic devices with extraordinary properties. We introduce a theoretical model for a field-effect transistor in which ions are the gated species instead of electrons. Our model incorporates readily-available soft materials, such as conductive porous membranes and polymer-electrolytes to represent a device that regulates ion currents and can be integrated as a component in larger circuits. By means of Nernst-Planck numerical simulations as well as an analytical description of the steady-state current we find that the responses of the system to various input voltages can be categorized into ohmic, sub-threshold, and active modes. This is fully analogous to what is known for the electronic field-effect transistor (FET). Pivotal FET properties such as the threshold voltage and the transconductance crucially depend on the half-cell redox potentials of the source and drain electrodes as well as on the polyelectrolyte charge density and the gate material work function. We confirm the analogy with the electronic FETs through numerical simulations of elementary amplifier circuits in which we successfully substitute the electronic transistor by an ionic transistor.

Single cell HaloChip assay on paper for point-of-care diagnosis.

PubMed

Ma, Liyuan; Qiao, Yong; Jones, Ross; Singh, Narendra; Su, Ming

2016-11-01

This article describes a paper-based low cost single cell HaloChip assay that can be used to assess drug- and radiation-induced DNA damage at point-of-care. Printing ink on paper effectively blocks fluorescence of paper materials, provides high affinity to charged polyelectrolytes, and prevents penetration of water in paper. After exposure to drug or ionizing radiation, cells are patterned on paper to create discrete and ordered single cell arrays, embedded inside an agarose gel, lysed with alkaline solution to allow damaged DNA fragments to diffuse out of nucleus cores, and form diffusing halos in the gel matrix. After staining DNA with a fluorescent dye, characteristic halos formed around cells, and the level of DNA damage can be quantified by determining sizes of halos and nucleus with an image processing program based on MATLAB. With its low fabrication cost and easy operation, this HaloChip on paper platform will be attractive to rapidly and accurately determine DNA damage for point-of-care evaluation of drug efficacy and radiation condition. Graphical Abstract Single cell HaloChip on paper.

Adsorption of polyelectrolyte-like proteins to silica surfaces and the impact of pH on the response to ionic strength. A Monte Carlo simulation and ellipsometry study.

PubMed

Hyltegren, Kristin; Skepö, Marie

2017-05-15

The adsorbed amount of the polyelectrolyte-like protein histatin 5 on a silica surface depends on the pH and the ionic strength of the solution. Interestingly, an increase in ionic strength affects the adsorbed amount differently depending on the pH of the solution, as shown by ellipsometry measurements (Hyltegren, 2016). We have tested the hypothesis that the same (qualitative) trends can be found also from a coarse-grained model that takes all charge-charge interactions into account within the frameworks of Gouy-Chapman and Debye-Hückel theories. Using the same coarse-grained model as in our previous Monte Carlo study of single protein adsorption (Hyltegren, 2016), simulations of systems with many histatin 5 molecules were performed and then compared with ellipsometry measurements. The strength of the short-ranged attractive interaction between the protein and the surface was varied. The coarse-grained model does not qualitatively reproduce the pH-dependence of the experimentally observed trends in adsorbed amount as a function of ionic strength. However, the simulations cast light on the balance between electrostatic attraction between protein and surface and electrostatic repulsion between adsorbed proteins, the deficiencies of the Langmuir isotherm, and the implications of protein charge regulation in concentrated systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Next-Generation Theranostic Agents Based on Polyelectrolyte Microcapsules Encoded with Semiconductor Nanocrystals: Development and Functional Characterization

NASA Astrophysics Data System (ADS)

Nifontova, Galina; Zvaigzne, Maria; Baryshnikova, Maria; Korostylev, Evgeny; Ramos-Gomes, Fernanda; Alves, Frauke; Nabiev, Igor; Sukhanova, Alyona

2018-01-01

Fabrication of polyelectrolyte microcapsules and their use as carriers of drugs, fluorescent labels, and metal nanoparticles is a promising approach to designing theranostic agents. Semiconductor quantum dots (QDs) are characterized by extremely high brightness and photostability that make them attractive fluorescent labels for visualization of intracellular penetration and delivery of such microcapsules. Here, we describe an approach to design, fabricate, and characterize physico-chemical and functional properties of polyelectrolyte microcapsules encoded with water-solubilized and stabilized with three-functional polyethylene glycol derivatives core/shell QDs. Developed microcapsules were characterized by dynamic light scattering, electrophoretic mobility, scanning electronic microscopy, and fluorescence and confocal microscopy approaches, providing exact data on their size distribution, surface charge, morphological, and optical characteristics. The fluorescence lifetimes of the QD-encoded microcapsules were also measured, and their dependence on time after preparation of the microcapsules was evaluated. The optimal content of QDs used for encoding procedure providing the optimal fluorescence properties of the encoded microcapsules was determined. Finally, the intracellular microcapsule uptake by murine macrophages was demonstrated, thus confirming the possibility of efficient use of developed system for live cell imaging and visualization of microcapsule transportation and delivery within the living cells.

Effects of conformational ordering on protein/polyelectrolyte electrostatic complexation: ionic binding and chain stiffening

PubMed Central

Cao, Yiping; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O.

2016-01-01

Coupling of electrostatic complexation with conformational transition is rather general in protein/polyelectrolyte interaction and has important implications in many biological processes and practical applications. This work studied the electrostatic complexation between κ-carrageenan (κ-car) and type B gelatin, and analyzed the effects of the conformational ordering of κ-car induced upon cooling in the presence of potassium chloride (KCl) or tetramethylammonium iodide (Me4NI). Experimental results showed that the effects of conformational ordering on protein/polyelectrolyte electrostatic complexation can be decomposed into ionic binding and chain stiffening. At the initial stage of conformational ordering, electrostatic complexation can be either suppressed or enhanced due to the ionic bindings of K+ and I− ions, which significantly alter the charge density of κ-car or occupy the binding sites of gelatin. Beyond a certain stage of conformational ordering, i.e., helix content θ > 0.30, the effect of chain stiffening, accompanied with a rapid increase in helix length ζ, becomes dominant and tends to dissociate the electrostatic complexation. The effect of chain stiffening can be theoretically interpreted in terms of double helix association. PMID:27030165

Thermodynamics, electrostatics, and ionic current in nanochannels grafted with pH-responsive end-charged polyelectrolyte brushes.

PubMed

Chen, Guang; Das, Siddhartha

2017-03-01

In this paper, we study the thermodynamics, electrostatics, and an external electric field driven ionic current in a pH-responsive, end-charged polyelectrolyte (PE) brush grafted nanochannel. By employing a mean field theory, we unravel a highly nonintuitive interplay of pH and electrolyte salt concentration in dictating the height of the end-charged PE brush. Larger pH or weak hydrogen ion concentration leads to maximum ionization of the charge-producing group-as a consequence, the resulting the electric double layer (EDL) energy get maximized causing a maximum deviation of the brush height from the value (d 0 ) of the uncharged brush. This deviation may result in enhancement or lowering of the brush height as compared to d 0 depending on whether the PE end locates lower or higher than h/2 (h is the nanochannel half height) and the salt concentration. Subsequently, we use this combined PE-brush-configuration-EDL-electrostatics framework to compute the ionic current in the nanochannel. We witness that the ionic current for smaller pH is much larger despite the corresponding magnitude of the EDL electrostatic potential being much smaller-this stems from the presence of a much larger concentration of H+ ions at small pH and the fact that H+ ions have very large mobilities. In fact, this ionic current shows a steep variation with pH that can be useful in exploring new designs for applications involving quantification and characterization of ionic current in PE-brush-grafted nanochannels. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Imaging trypsin activity through changes in the orientation of liquid crystals coupled to the interactions between a polyelectrolyte and a phospholipid layer.

PubMed

Hu, Qiong-Zheng; Jang, Chang-Hyun

2012-03-01

In this study, we developed a new type of liquid crystal (LC)-based sensor for the real-time and label-free monitoring of enzymatic activity through changes in the orientation of LCs coupled to the interactions between polyelectrolyte and phospholipid. The LCs changed from dark to bright after an aqueous solution of poly-l-lysine (PLL) was transferred onto a self-assembled monolayer of the phospholipid, dioleoyl-sn-glycero-3-phospho-rac-(1-glycerol) sodium salt (DOPG), at the aqueous/LC interface. Interactions between the positively charged PLL and the negatively charged DOPG drove the reorganization of the phospholipid membrane, which induced an orientational transition in the LCs from a homeotropic to planar state. Since the serine endopeptidase trypsin can enzymatically catalyze the hydrolysis of PLL, the dark-to-bright shift in the optical response was not observed after transferring a mixed solution of PLL and trypsin onto the DOPG-decorated LC interface, indicating that no orientational transitions in the LCs occurred. However, the optical response from dark to bright was observed when the mixture in the optical cell was replaced by an aqueous solution of PLL. Control experiments with trypsin or an aqueous mixture of PLL and deactivated trypsin further confirmed the feasibility of this approach. The detection limit of trypsin was determined to be ~1 μg/mL. This approach holds great promise for use in the development of LC-based sensors for the detection of enzymatic reactions in cases where the biological polyelectrolyte substrates of enzymes could disrupt the organization of the membrane and induce orientational transitions of LCs at the aqueous/LC interface. © 2012 American Chemical Society

Role of Electrostatic Interactions on the Transport of Druglike Molecules in Hydrogel-Based Articular Cartilage Mimics: Implications for Drug Delivery.

PubMed

Ye, Fengbin; Baldursdottir, Stefania; Hvidt, Søren; Jensen, Henrik; Larsen, Susan W; Yaghmur, Anan; Larsen, Claus; Østergaard, Jesper

2016-03-07

In the field of drug delivery to the articular cartilage, it is advantageous to apply artificial tissue models as surrogates of cartilage for investigating drug transport and release properties. In this study, artificial cartilage models consisting of 0.5% (w/v) agarose gel containing 0.5% (w/v) chondroitin sulfate or 0.5% (w/v) hyaluronic acid were developed, and their rheological and morphological properties were characterized. UV imaging was utilized to quantify the transport properties of the following four model compounds in the agarose gel and in the developed artificial cartilage models: H-Ala-β-naphthylamide, H-Lys-Lys-β-naphthylamide, lysozyme, and α-lactalbumin. The obtained results showed that the incorporation of the polyelectrolytes chondroitin sulfate or hyaluronic acid into agarose gel induced a significant reduction in the apparent diffusivities of the cationic model compounds as compared to the pure agarose gel. The decrease in apparent diffusivity of the cationic compounds was not caused by a change in the gel structure since a similar reduction in apparent diffusivity was not observed for the net negatively charged protein α-lactalbumin. The apparent diffusivity of the cationic compounds in the negatively charged hydrogels was highly dependent on the ionic strength, pointing out the importance of electrostatic interactions between the diffusant and the polyelectrolytes. Solution based affinity studies between the model compounds and the two investigated polyelectrolytes further confirmed the electrostatic nature of their interactions. The results obtained from the UV imaging diffusion studies are important for understanding the effect of drug physicochemical properties on the transport in articular cartilage. The extracted information may be useful in the development of hydrogels for in vitro release testing having features resembling the articular cartilage.

Atomistic Molecular Dynamics Simulations of the Electrical Double

NASA Astrophysics Data System (ADS)

Li, Zifeng; Milner, Scott; Fichthorn, Kristen

2015-03-01

The electrical double layer (EDL) near the polymer/water interface plays a key role in the colloidal stability of latex paint. To elucidate the structure of the EDL at the molecular level, we conducted an all-atom molecular dynamics simulations. We studied two representative surface charge groups in latex, the ionic surfactant sodium dodecyl sulfate (SDS) and the grafted short polyelectrolyte charged by dissociated methyl methacrylic acid (MAA) monomers. Our results confirm that the Poisson-Boltzmann theory works well outside the Stern layer. Our calculated electrostatic potential at the Outer Helmholtz Plane (OHP) is close to the zeta potential measured experimentally, which suggests that the potential at the OHP is a good estimate of the zeta potential. We found that the position of the OHP for the MAA polyelectrolyte system extends much further into the aqueous phase than that in the SDS system, resulting in a Stern layer that is twice as thick. This model will allow for future investigations of the interactions of the surface with different surfactants and rheology modifiers, which may serve as a guide to tune the rheology of latex formulations. We thank Dow Chemical Company for financial support.

Swelling of biological and semiflexible polyelectrolytes.

PubMed

Dobrynin, Andrey V; Carrillo, Jan-Michael Y

2009-10-21

We have developed a theoretical model of swelling of semiflexible (biological) polyelectrolytes in salt solutions. Our approach is based on separation of length scales which allowed us to split a chain's electrostatic energy into two parts that describe local and remote electrostatic interactions along the polymer backbone. The local part takes into account interactions between charged monomers that are separated by distances along the polymer backbone shorter than the chain's persistence length. These electrostatic interactions renormalize chain persistence length. The second part includes electrostatic interactions between remote charged pairs along the polymer backbone located at distances larger than the chain persistence length. These interactions are responsible for chain swelling. In the framework of this approach we calculated effective chain persistence length and chain size as a function of the Debye screening length, chain degree of ionization, bare persistence length and chain degree of polymerization. Our crossover expression for the effective chain's persistence length is in good quantitative agreement with the experimental data on DNA. We have been able to fit experimental datasets by using two adjustable parameters: DNA ionization degree (α = 0.15-0.17) and a bare persistence length (l(p) = 40-44 nm).

Excluded volume and ion-ion correlation effects on the ionic atmosphere around B-DNA: Theory, simulations, and experiments

PubMed Central

Ovanesyan, Zaven; Fenley, Marcia O.; Guerrero-García, Guillermo Iván; Olvera de la Cruz, Mónica

2014-01-01

The ionic atmosphere around a nucleic acid regulates its stability in aqueous salt solutions. One major source of complexity in biological activities involving nucleic acids arises from the strong influence of the surrounding ions and water molecules on their structural and thermodynamic properties. Here, we implement a classical density functional theory for cylindrical polyelectrolytes embedded in aqueous electrolytes containing explicit (neutral hard sphere) water molecules at experimental solvent concentrations. Our approach allows us to include ion correlations as well as solvent and ion excluded volume effects for studying the structural and thermodynamic properties of highly charged cylindrical polyelectrolytes. Several models of size and charge asymmetric mixtures of aqueous electrolytes at physiological concentrations are studied. Our results are in good agreement with Monte Carlo simulations. Our numerical calculations display significant differences in the ion density profiles for the different aqueous electrolyte models studied. However, similar results regarding the excess number of ions adsorbed to the B-DNA molecule are predicted by our theoretical approach for different aqueous electrolyte models. These findings suggest that ion counting experimental data should not be used alone to validate the performance of aqueous DNA-electrolyte models. PMID:25494770

Significance of Algal Polymer in Designing Amphotericin B Nanoparticles

PubMed Central

Bhatia, Saurabh; Kumar, Vikash; Sharma, Kiran; Nagpal, Kalpana; Bera, Tanmoy

2014-01-01

Development of oral amphotericin B (AmB) loaded nanoparticles (NPs) demands a novel technique which reduces its toxicity and other associated problems. Packing of AmB in between two oppositely charged ions by polyelectrolyte complexation technique proved to be a successful strategy. We have developed a novel carrier system in form of polyelectrolyte complex of AmB by using chitosan (CS) and porphyran (POR) as two oppositely charged polymers with TPP as a crosslinking agent. Initially POR was isolated from Porphyra vietnamensis followed by the fact that its alkali induced safe reduction in molecular weight was achieved. Formulation was optimized using three-factor three-level (33) central composite design. High concentration of POR in NPs was confirmed by sulfated polysaccharide (SP) assay. Degradation and dissolution studies suggested the stability of NPs over wide pH range. Hemolytic toxicity data suggested the safety of prepared formulation. In vivo and in vitro antifungal activity demonstrated the high antifungal potential of optimized formulation when compared with standard drug and marketed formulations. Throughout the study TPP addition did not cause any significant changes. Therefore, these experimental oral NPs may represent an interesting carrier system for the delivery of AmB. PMID:25478596

Monte Carlo simulations of flexible polyanions complexing with whey proteins at their isoelectric point

NASA Astrophysics Data System (ADS)

de Vries, R.

2004-02-01

Electrostatic complexation of flexible polyanions with the whey proteins α-lactalbumin and β-lactoglobulin is studied using Monte Carlo simulations. The proteins are considered at their respective isoelectric points. Discrete charges on the model polyelectrolytes and proteins interact through Debye-Hückel potentials. Protein excluded volume is taken into account through a coarse-grained model of the protein shape. Consistent with experimental results, it is found that α-lactalbumin complexes much more strongly than β-lactoglobulin. For α-lactalbumin, strong complexation is due to localized binding to a single large positive "charge patch," whereas for β-lactoglobulin, weak complexation is due to diffuse binding to multiple smaller charge patches.

Nucleic acid polymeric properties and electrostatics: Directly comparing theory and simulation with experiment.

PubMed

Sim, Adelene Y L

2016-06-01

Nucleic acids are biopolymers that carry genetic information and are also involved in various gene regulation functions such as gene silencing and protein translation. Because of their negatively charged backbones, nucleic acids are polyelectrolytes. To adequately understand nucleic acid folding and function, we need to properly describe its i) polymer/polyelectrolyte properties and ii) associating ion atmosphere. While various theories and simulation models have been developed to describe nucleic acids and the ions around them, many of these theories/simulations have not been well evaluated due to complexities in comparison with experiment. In this review, I discuss some recent experiments that have been strategically designed for straightforward comparison with theories and simulation models. Such data serve as excellent benchmarks to identify limitations in prevailing theories and simulation parameters. Copyright © 2015 Elsevier B.V. All rights reserved.

Interaction between two polyelectrolyte brushes.

PubMed

Kumar, N Arun; Seidel, Christian

2007-08-01

We report molecular dynamics simulations on completely charged polyelectrolyte brushes grafted to two parallel surfaces. The pressure Pi is evaluated as a function of separation D between the two grafting planes. For decreasing separation, Pi shows several regimes distinguished by their scaling with D which reflects the different physical nature of the various regimes. At weak compression the pressure obeys the 1D power law predicted by scaling theory of an ideal gas of counterions in the osmotic brush regime. In addition we find that the brushes shrink as they approach each other trying to avoid interpenetration. At higher compressions where excluded volume interactions become important, we obtain scaling exponents between -2 at small grafting density rho(a) and -3 at large rho(a). This behavior indicates a transition from a brush under good solvent condition to the melt regime with increasing grafting density.

Self-assembled graphene/azo polyelectrolyte multilayer film and its application in electrochemical energy storage device.

PubMed

Wang, Dongrui; Wang, Xiaogong

2011-03-01

Graphene/azo polyelectrolyte multilayer films were fabricated through electrostatic layer-by-layer (LbL) self-assembly, and their performance as electrochemical capacitor electrode was investigated. Cationic azo polyelectrolyte (QP4VP-co-PCN) was synthesized through radical polymerization, postpolymerization azo coupling reaction, and quaternization. Negatively charged graphene nanosheets were prepared by a chemically modified method. The LbL films were obtained by alternately dipping a piece of the pretreated substrates in the QP4VP-co-PCN and nanosheet solutions. The processes were repeated until the films with required numbers of bilayers were obtained. The self-assembly and multilayer surface morphology were characterized by UV-vis spectroscopy, AFM, SEM, and TEM. The performance of the LbL films as electrochemical capacitor electrode was estimated using cyclic voltammetry. Results show that the graphene nanosheets are densely packed in the multilayers and form random graphene network. The azo polyelectrolyte cohesively interacts with the nanosheets in the multilayer structure, which prevents agglomeration of graphene nanosheets. The sheet resistance of the LbL films decreases with the increase of the layer numbers and reaches the stationary value of 1.0 × 10(6) Ω/square for the film with 15 bilayers. At a scanning rate of 50 mV/s, the LbL film with 9 bilayers shows a gravimetric specific capacitance of 49 F/g in 1.0 M Na(2)SO(4) solution. The LbL films developed in this work could be a promising type of the electrode materials for electric energy storage devices.

Kinetic Modulation of Pulsed Chrono-potentiometric Polymeric Membrane Ion Sensors by Polyelectrolyte Multilayers

PubMed Central

Xu, Yida; Xu, Chao; Shvarev, Alexey; Becker, Thomas; De Marco, Roland

2010-01-01

Polymeric membrane ion selective electrodes are normally interrogated by zero current potentiometry, and their selectivity is understood to be primarily dependent on an extraction/ion-exchange equilibrium between the aqueous sample and polymeric membrane. If concentration gradients in the contacting diffusion layers are insubstantial, the membrane response is thought to be rather independent of kinetic processes such as surface blocking effects. In this work, the surface of calcium-selective polymeric ion-selective electrodes is coated with polyelectrolyte multilayers as evidenced by zeta potential measurements, atomic force microscopy and electrochemical impedance spectroscopy. Indeed, such multilayers have no effect on their potentiometric response if the membranes are formulated in a traditional manner, containing a lipophilic ion-exchanger and a calcium-selective ionophore. However, drastic changes in the potential response are observed if the membranes are operated in a recently introduced kinetic mode using pulsed chronopotentiometry. The results suggest that the assembled nanostructured multilayers drastically alter the kinetics of ion transport to the sensing membrane, making use of the effect that polyelectrolyte multilayers have different permeabilities toward ions with different valences. The results have implications to the design of chemically selective ion sensors since surface localized kinetic limitations can now be used as an additional dimension to tune the operational ion selectivity. PMID:17711298

Multiscale Simulations of Barrier and Aging Properties of Polymer Nanocomposites

DTIC Science & Technology

2013-10-29

Complexation Between Weakly Basic Dendrimers and Linear Polyelectrolytes: Effects of Chain Stiffness, Grafts, and pOH,” Thomas Lewis, Gunja Pandav, Ahmad Omar...November 2012. (c) Presentations 20.0010/29/2013 Venkat Ganesan, Thomas Lewis. Interactions between Grafted Cationic Dendrimers and Anionic Bilayer... dendrimers have shown great promise in drug and gene therapy applications. Despite the advantages realized through positively charged dendrimers , a

Towards biocompatible vaccine delivery systems: interactions of colloidal PECs based on polysaccharides with HIV-1 p24 antigen.

PubMed

Drogoz, Alexandre; Munier, Séverine; Verrier, Bernard; David, Laurent; Domard, Alain; Delair, Thierry

2008-02-01

This work reports on the interactions of a model protein (p24, the capside protein of HIV-1 virus) with colloids obtained from polyelectrolyte complexes (PECs) involving two polysaccharides: chitosan and dextran sulfate (DS). The PECs were elaborated by a one-shot addition of default amounts of one counterpart to the polymer in excess. Depending on the nature of the excess polyelectrolyte, the submicrometric colloid was either positively or negatively charged. HIV-1 capsid p24 protein was chosen as antigen, the ultrapure form, lipopolysaccharide-free (endotoxin-, vaccine grade) was used in most experiments, as the level of purity of the protein had a great impact on the immobilization process. p24 sorption kinetics, isotherms, and loading capacities were investigated for positively and negatively charged particles of chitosans and dextran sulfates differing in degrees of polymerization (DP) or acetylation (DA). Compared with the positive particles, negatively charged colloids had higher binding capacities, faster kinetics, and a better stability of the adsorbed p24. Capacities up to 600 mg x g(-1) (protein-colloid) were obtained, suggesting that the protein interacted within the shell of the particles. Small-angle X-rays scattering experiments confirmed this hypothesis. Finally, the immunogenicity of the p24-covered particles was assessed for vaccine purposes in mice. The antibody titers obtained with immobilized p24 was dose dependent and in the same range as for Freund's adjuvant, a gold standard for humoral responses.

The Role of Hydrophobicity in the Cellular Uptake of Negatively Charged Macromolecules.

PubMed

Abou Matar, Tamara; Karam, Pierre

2018-02-01

It is generally accepted that positively charged molecules are the gold standard to by-pass the negatively charged cell membrane. Here, it is shown that cellular uptake is also possible for polymers with negatively charged side chains and hydrophobic backbones. Specifically, poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene], a conjugated polyelectrolyte with sulfonate, as water-soluble functional groups, is shown to accumulate in the intracellular region. When the polymer hydrophobic backbone is dissolved using polyvinylpyrrolidone, an amphiphilic macromolecule, the cellular uptake is dramatically reduced. The report sheds light on the fine balance between negatively charged side groups and the hydrophobicity of polymers to either enhance or reduce cellular uptake. As a result, these findings will have important ramifications on the future design of targeted cellular delivery nanocarriers for imaging and therapeutic applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[An electron microscopy study of the structure of polyelectrolyte microcapsules containing protein and containing no protein].

PubMed

Kazakova, L I; Dubrovskiĭ, A V; Moshkov, D A; Shabarchina, L I; Sukhorukov, B I

2007-01-01

Electron micrographs of ultrathin sections of polyelectrolyte microparticles containing protein and free from protein for the formation of which CaCO3 spherulites served as a core basis have been obtained and analyzed. Polyelectrolyte microparticles with the number of alternately layered polyelectrolyte layers of polystyrene sulfonate and polyallylamine from 6 to 11 have been studied. It follows from the data obtained that protein-free polyelectrolyte particles having the dimensions 4.5-5 mm are formations of an intricate internal organization, which consist of a set of threadlike and closed nanoelements of polyelectrolyte nature with a thickness of 20-30 nm. The particles containing six to eight polyelectrolyte layers lack the external envelope; therefore, they were called polyelectrolyte microspherulites. With the number of layers nine and more, when a polyelectrolyte envelope appears on the surface, they transfer into polyelectrolyte microcapsules. It was found that, in a protein-containing polyelectrolyte microcapsule, as distinct from protein-free polyelectrolyte microspherulite and microcapsule, polyelectrolytes are located only in the nearsurface layer, and the external spatially organized envelope restricts the internal volume filled with protein solution. As the number of polyelectrolyte layers increases, the thickness of the envelope increases. The reasons for such substantial differences in the structures of polyelectrolyte microcapsules formed on protein-containing and protein-free CaCO3 spherulite are discussed.

Electrical properties of multilayers from low- and high-molecular-weight polyelectrolytes.

PubMed

Radeva, Tsetska; Milkova, Viktoria; Petkanchin, Ivana

2004-11-15

The formation of stable multilayer films by using as constituents sodium poly(4-styrene sulfonate) (PSS) and poly(4-vinyl pyridine) (PVP) was studied by electrooptics. A strong increase in basicity of the pyridine rings in the electrical field of the oppositely charged PSS chains was suggested to be the driving force for multilayer film formation. A linear increase in the film thickness was registered after deposition of the first three layers, with no dependence on the polyelectrolyte molecular weight. The electrooptical effect was found to increase with increasing area of each next layer, but depended on the molecular weights of both polymers. Polarization of "condensed" counterions along the chains of the last-adsorbed layer was suggested to explain this dependence. Following the counterion dynamics, we come to the conclusion that the electrical properties of the top layer govern the electrooptical behavior of the PSS/PVP film.

Monte Carlo simulations of flexible polyanions complexing with whey proteins at their isoelectric point.

PubMed

de Vries, R

2004-02-15

Electrostatic complexation of flexible polyanions with the whey proteins alpha-lactalbumin and beta-lactoglobulin is studied using Monte Carlo simulations. The proteins are considered at their respective isoelectric points. Discrete charges on the model polyelectrolytes and proteins interact through Debye-Huckel potentials. Protein excluded volume is taken into account through a coarse-grained model of the protein shape. Consistent with experimental results, it is found that alpha-lactalbumin complexes much more strongly than beta-lactoglobulin. For alpha-lactalbumin, strong complexation is due to localized binding to a single large positive "charge patch," whereas for beta-lactoglobulin, weak complexation is due to diffuse binding to multiple smaller charge patches. Copyright 2004 American Institute of Physics

Biocompatible Polymeric Nanoparticles as Promising Candidates for Drug Delivery.

PubMed

Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof; Błasiak, Ewa; Dziedzicka-Wasylewska, Marta

2015-06-16

The use of polymeric nanoparticles (NPs) in pharmacology provides many benefits because this approach can increase the efficacy and selectivity of active compounds. However, development of new nanocarriers requires better understanding of the interactions between NPs and the immune system, allowing for the optimization of NP properties for effective drug delivery. Therefore, in the present study, we focused on the investigation of the interactions between biocompatible polymeric NPs and a murine macrophage cell line (RAW 264.7) and a human monocytic leukemia cell line (THP-1). NPs based on a liquid core with polyelectrolyte shells were prepared by sequential adsorption of polyelectrolytes (LbL) using AOT (docusate sodium salt) as the emulsifier and the biocompatible polyelectrolytes polyanion PGA (poly-l-glutamic acid sodium salt) and polycation PLL (poly l-lysine). The average size of the obtained NPs was 80 nm. Pegylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG poly(ethylene glycol)). The influence of the physicochemical properties of the NPs (charge, size, surface modification) on viability, phagocytosis potential, and endocytosis was studied. Internalization of NPs was determined by flow cytometry and confocal microscopy. Moreover, we evaluated whether addition of PEG chains downregulates particle uptake by phagocytic cells. The presented results confirm that the obtained PEG-grafted NPs are promising candidates for drug delivery.

Encapsidation of Linear Polyelectrolyte in a Viral Nanocontainer

NASA Astrophysics Data System (ADS)

Hu, Yufang

2005-03-01

We present the results from a combined experimental and theoretical study on the self-assembly of a model icosahedral virus, Cowpea Chlorotic Mottle Virus (CCMV). The formation of native CCMV capsids is believed to be driven primarily by the electrostatic interactions between the viral RNA and the positively charged capsid interior, as well as by the hydrophobic interactions between capsid protein subunits. To probe these molecular interactions, in vitro self-assembly reactions are carried out using the CCMV capsid protein and a synthetic linear polyelectrolyte, sodium polystyrene sulfonate (NaPSS), which functions as the analog of viral RNA. Under appropriate solutions conditions, NaPSS is encapsidated by the viral capsid. The molecular weight of NaPSS is systematically varied and the resulting average capsid size, size distribution, and particle morphology are measured by transmission electron microscopy. The correlation between capsid size and packaged cargo size, as well as the upper limit of capsid packaging capacity, are characterized. To elucidate the physical role played by the encapsidated polyelectrolyte in determining the preferred size of spherical viruses, we have used a mean-field approach to calculate the free energy of the virus-like particle as a function of chain length (and of the strength of chain/capsid attractive interaction). We find good agreement with our analytical calculations and experimental results.

Highly structured and surface modified poly(epsilon-caprolactone) scaffolds derived from co-continuous polymer blends for bone tissue engineering

NASA Astrophysics Data System (ADS)

Mehr, Nima Ghavidel

Chitosan, an important member of the polysaccharide family was used to alter the chemistry of PCL scaffolds and bring hydrophilicity to the surface. The deposition of a homogeneous chitosan layer on the surface of the PCL scaffolds was carried out using a Layer-by-Layer (LbL) selfassembly of poly(dialyldemethylammunium chloride) (PDADMAC) as cationic and poly(sodium 4-styrenesulfonate) (PSS) as anionic polyelectrolytes. The final negatively charged PSS layer allows for the addition of the positively charged chitosan as the outermost layer. Gravimetric measurements revealed that the addition of up to 3 layers leads to the formation of interdiffusing polyelectrolyte layers which do not allow for the formation of defined positive or negative charges. By increasing the number of polyelectrolyte layers with alternating charges, more welldefined layers are formed. Detailed analyses of O/C, N/C and S/C ratios by X-ray photoelectron spectroscopy (XPS) show that the PSS molecule dominates the surface as the last deposited polyelectrolyte layer at higher number of depositions (n=8), which can later be the surface for the deposition of chitosan. The LbL deposition of the chitosan layer on the LbL coating was then shown to be locally homogeneous at different depths within the scaffolds which also clarified that the LbL method is superior to the dip coating strategy. SEM analysis showed that there is a rough chitosan surface on the 2D solid PCL constructs whose thickness ranges from 550-700 nanometers. These results demonstrate that the application of LbL self-assembly of polyelectrolytes followed by the addition of chitosan as the outermost layer provides a route towards stable and homogeneous surface modification and has the potential to transform a classic fully interconnected porous synthetic polymer material to one with essentially complete chitosanlike surface characteristics. The osteogenic potential of PCL scaffolds with a chitosan coating using Layer-by-Layer (LbL) surface modification has never been evaluated before. This part of the study tests the hypothesis that in vitro osteogenesis can be achieved in 3D PCL scaffolds with fully interconnected pores of 84 im or 141 im average diameter and biomineralization can be enhanced when pore surfaces are coated with chitosan adsorbed to LbL deposited polyelectrolytes. In order to reduce the errors originating from cell infiltration inefficiencies, the most competent cell seeding protocol has to be defined. Among classical cell seeding at 37°C, 2-step seeding at 37°C and cold seeding at 4°C in a medium containing 2% FBS, the last strategy proved to yield the best population of freshly trypsinized hBMSCs at all depths of the 1mm-thick scaffolds. hBMSCs cold-seeded in PCL scaffolds with or without an LbL-chitosan coating were cultured for 10 days in proliferation medium, followed by 21 days in osteogenic medium. At day 2, MSCs formed sparse monolayers with rounded cell morphologies with thin filopodia anchored to the unmodified PCL, as compared to more spread cells on chitosan-coated pore surfaces. At day 10, cells proliferated as an external layer, and migrated onto secreted collagen networks that filled the interpore spaces of all scaffolds, but only adhered to chitosan-coated pore surfaces. At day 31, similar levels of tissue formed in scaffolds with and without chitosan, but more tissue was deposited in the outer pores than the inner pores. Furthermore, more biomineralized matrix was observed in the inner 84 im chitosan-coated pores (p<0.05). In the PCL-only samples, haphazard mineral deposits were observed in highly colonized outer layers and in the inner 141 im pores. MSCs cultured on chitosan-coated 2D control surfaces show higher alkaline phosphatase staining but negligible mineralization. This study showed that hBMSCs survive, proliferate, and attach to fibrotic matrix rather than the PCL-only scaffold pore surfaces. LbL-chitosan-coated scaffolds showed more biomineralization in 3D inner 84 im pores, a cell response that may be related to surface curvature in addition to improved surface hydrophilicity. (Abstract shortened by UMI.).

Influence of natural organic matter (NOM) and synthetic polyelectrolytes on colloidal behavior of metal oxide nanoparticles

NASA Astrophysics Data System (ADS)

Ghosh, Saikat

The colloidal behavior of engineered nanomaterials exposed in an aquatic environment may significantly influence their bioavailability as well as toxicity to different species. Natural organic matter (NOM) is one of the major colloidal materials ubiquitous in the environment with significant structural heterogeneity. Therefore, role of NOM molecules on environmental fate of these engineered NPs needs to be addressed. Colloidal behavior of aluminum (Al2O 3) and magnetic iron oxide (gammaFe2O3) NPs was studied in the presence of structurally different HAs and synthetic polyacrylic acids (PAAs). The conformation behavior of the adsorobed NOM/polyelectrolyte under specific solution conditions were determined with dynamic light scattering, atomic force microscopy measurements. Al2O3 NPs followed the classical DLVO model of colloidal behavior in their pristine state. However, a significant deviation from the classical DLVO model was observed when these NPs were coated with structurally different HAs. Low polar, high molecular weight HA fractions showed much stronger stabilization against Ca2+ induced aggregation. Previously, we observed that these low polar, high molecular weight fractions strongly destabilized the NP suspension when added in a small quantity. A significant transformation in suspension stability was observed possibly due to steric effect of these adsorbed HAs. The colloidal behavior of PAA/NOM coated ferrimagnetic gammaFe 2O3 NPs were investigated. Pure gammaFe2O 3 NPs were extremely unstable in aqueous solution but a significant enhancement in colloidal stability was observed after coating with polyelectrolytes/NOM. The steric as well as electrostatic stabilization introduced by the polyelectrolyte coating strongly dictated the colloidal stability. The alteration of electrosteric stabilization mechanisms by pH-induced conformation change profoundly influences the colloidal stability. Atomic force microscopy (AFM) study revealed a highly stretched conformation of the HA molecular chains adsorbed on gammaFe 2O3 NP surface with increasing pH from 5 to 9 which enhanced the colloidal stability trough long range electrosteric stabilization. The depletion of the polyelectrolytes during dilution of the suspension in the acidic solution conditions and in the presence of Na+ or Ca 2+ decreased the colloidal stability. The conformation of the polyelectrolytes adsorbed on the NP surface altered significantly as a function of substrate surface charge as viewed from the AFM imaging.

A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template-Assisted Assembly of Polyfluorene Nanowires.

PubMed

Bae, Dong Geun; Jeong, Ji-Eun; Kang, Seok Hee; Byun, Myunghwan; Han, Dong-Wook; Lin, Zhiqun; Woo, Han Young; Hong, Suck Won

2016-08-01

DNA molecules have been widely recognized as promising building blocks for constructing functional nanostructures with two main features, that is, self-assembly and rich chemical functionality. The intrinsic feature size of DNA makes it attractive for creating versatile nanostructures. Moreover, the ease of access to tune the surface of DNA by chemical functionalization offers numerous opportunities for many applications. Herein, a simple yet robust strategy is developed to yield the self-assembly of DNA by exploiting controlled evaporative assembly of DNA solution in a unique confined geometry. Intriguingly, depending on the concentration of DNA solution, highly aligned nanostructured fibrillar-like arrays and well-positioned concentric ring-like superstructures composed of DNAs are formed. Subsequently, the ring-like negatively charged DNA superstructures are employed as template to produce conductive organic nanowires on a silicon substrate by complexing with a positively charged conjugated polyelectrolyte poly[9,9-bis(6'-N,N,N-trimethylammoniumhexyl)fluorene dibromide] (PF2) through the strong electrostatic interaction. Finally, a monolithic integration of aligned arrays of DNA-templated PF2 nanowires to yield two DNA/PF2-based devices is demonstrated. It is envisioned that this strategy can be readily extended to pattern other biomolecules and may render a broad range of potential applications from the nucleotide sequence and hybridization as recognition events to transducing elements in chemical sensors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous Production of Discrete Plasmid DNA-Polycation Nanoparticles Using Flash Nanocomplexation.

PubMed

Santos, Jose Luis; Ren, Yong; Vandermark, John; Archang, Maani M; Williford, John-Michael; Liu, Heng-Wen; Lee, Jason; Wang, Tza-Huei; Mao, Hai-Quan

2016-12-01

Despite successful demonstration of linear polyethyleneimine (lPEI) as an effective carrier for a wide range of gene medicine, including DNA plasmids, small interfering RNAs, mRNAs, etc., and continuous improvement of the physical properties and biological performance of the polyelectrolyte complex nanoparticles prepared from lPEI and nucleic acids, there still exist major challenges to produce these nanocomplexes in a scalable manner, particularly for lPEI/DNA nanoparticles. This has significantly hindered the progress toward clinical translation of these nanoparticle-based gene medicine. Here the authors report a flash nanocomplexation (FNC) method that achieves continuous production of lPEI/plasmid DNA nanoparticles with narrow size distribution using a confined impinging jet device. The method involves the complex coacervation of negatively charged DNA plasmid and positive charged lPEI under rapid, highly dynamic, and homogeneous mixing conditions, producing polyelectrolyte complex nanoparticles with narrow distribution of particle size and shape. The average number of plasmid DNA packaged per nanoparticles and its distribution are similar between the FNC method and the small-scale batch mixing method. In addition, the nanoparticles prepared by these two methods exhibit similar cell transfection efficiency. These results confirm that FNC is an effective and scalable method that can produce well-controlled lPEI/plasmid DNA nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of methyl groups on conformational properties of small ionized comb-like polyelectrolytes at the atomic level.

PubMed

Zhao, Hongxia; Liu, Jiaping; Ran, Qianping; Yang, Yong; Shu, Xin

2017-03-01

Comb-like polycarboxylate ether (PCE) molecules with different content of methyl groups substituted on backbone and different location of methyl groups substituted on the side chains, respectively, were designed and were studied in explicit salt solutions by all-atom molecular dynamics simulations. Methyl groups substituted on the backbone of PCE have a great effect on the conformation of PCE. Stiffness of charged backbone was not only affected by the rotational freedom but also the electrostatic repulsion between the charged COO - groups. The interaction of counterions (Na + ) with COO - groups for PCE3 (with part of AA substituted by MAA on the backbone) was stronger and the screen effect was great, which decided the smaller size of PCE3. The interaction between water and COO - groups was strong regardless of the content of AA substituted by MAA on the backbone. The effect of methyl groups substituted on the different location of side chains on the conformation of PCE was less than that of methyl groups substituted on the backbone. The equilibrium sizes of the four PCE molecules with methyl groups substituted on the side chains were similar. Graphical Abstract Effect of methyl groups on conformational properties of small ionized comb-like polyelectrolytes at the atomic level.

Removal of copper ions from aqueous solution by adsorption onto novel polyelectrolyte film-coated nanofibrous silk fibroin non-wovens

NASA Astrophysics Data System (ADS)

Zhou, Weitao; Huang, Haitao; Du, Shan; Huo, Yingdong; He, Jianxin; Cui, Shizhong

2015-08-01

In this approach, polyelectrolyte film-coated nanofibrous silk fibroin (SF) nonwovens were prepared from the alternate deposition of positively charged polyethylenimine (PEI) and negatively charged SF using electrostatic layer-by-layer (LBL) self-assembled technology. The composite membranes were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectrometer. The SF-PEI multilayer-assembled nanofibers (less than five layers) were fine and uniform with the fiber diameter from 400 nm to 600 nm, and had very large surface area and high porosity (more than 70%). The amino groups of PEI were proved to be deposited onto SF nonwovens, which granted the coated nonwovens with potential applicability for copper ions adsorption. The PEI films coated SF substrate showed much higher copper ions adsorption capacity than that of ethanol treated SF nanofibers. Adding the number of PEI coated could enhance the Cu2+ adsorption capacity significantly. The maximum milligrams per gram of copper ions adsorbed reached 59.7 mg/g when the SF substrate was coated with 5 bilayers of SF-PEI. However, the copper ions adsorption capacity had no obvious change as the number of PEI continued to increase. These results suggest potential for PEL film-coated nanofibrous nonwovens as a new adsorbent for metal ions.

Continuous Production of Discrete Plasmid DNA-Polycation Nanoparticles Using Flash Nanocomplexation

PubMed Central

Santos, Jose Luis; Ren, Yong; Vandermark, John; Archang, Maani M.; Williford, John-Michael; Liu, Heng-wen; Lee, Jason; Wang, Tza-Huei; Mao, Hai-Quan

2016-01-01

Despite successful demonstration of linear polyethyleneimine (lPEI) as an effective carrier for a wide range of gene medicine, including DNA plasmids, small interfering RNAs, mRNAs, etc., and continuous improvement of the physical properties and biological performance of the polyelectrolyte complex nanoparticles prepared from lPEI and nucleic acids, there still exist major challenges to produce these nanocomplexes in a scalable manner, particularly for lPEI/DNA nanoparticles. This has significantly hindered the progress towards clinical translation of these nanoparticle-based gene medicine. Here we report a flash nanocomplexation (FNC) method that achieves continuous production of lPEI/plasmid DNA nanoparticles with narrow size distribution using a confined impinging jet device. The method involves the complex coacervation of negatively charged DNA plasmid and positive charged lPEI under rapid, highly dynamic, and homogeneous mixing conditions, producing polyelectrolyte complex nanoparticles with narrow distribution of particle size and shape. The average number of plasmid DNA packaged per nanoparticles and its distribution are similar between the FNC method and the small-scale batch mixing method. In addition, the nanoparticles prepared by these two methods exhibit similar cell transfection efficiency. These results confirm that FNC is an effective and scalable method that can produce well-controlled lPEI/plasmid DNA nanoparticles. PMID:27717227

Self-assembled carrageenan/protamine polyelectrolyte nanoplexes-Investigation of critical parameters governing their formation and characteristics.

PubMed

Dul, Maria; Paluch, Krzysztof J; Kelly, Hazel; Healy, Anne Marie; Sasse, Astrid; Tajber, Lidia

2015-06-05

The aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electric double layer electrostatics of pH-responsive spherical polyelectrolyte brushes in the decoupled regime.

PubMed

Li, Hao; Chen, Guang; Das, Siddhartha

2016-11-01

Understanding the behavior and properties of spherical polyelectrolyte brushes (SPEBs), which are polyelectrolyte brushes grafted to a spherical core, is fundamental to many applications in biomedical, chemical and petroleum engineering as well as in pharmaceutics. In this paper, we study the pH-responsive electrostatics of such SPEBs in the decoupled regime. In the first part of the paper, we derive the scaling conditions in terms of the grafting density of the PEs on the spherical core that ensure that the analysis can be performed in the decoupled regime. In such a regime the elastic and the excluded volume effects of polyelectrolyte brushes (PEBs) can be decoupled from the electrostatic effects associated with the PE charge and the induced EDL. As a consequence the PE brush height, assumed to be dictated by the balance of the elastic and excluded volume effects, can be independent of the electrostatic effects. In the second part, we quantify the pH-responsive electrostatics of the SPEBs - we pinpoint that the radial monomer distribution for a given brush molecule exhibit a non-unique cubic distribution that decays away from the spherical core. Such a monomer distribution ensures that the hydrogen ion concentration is appropriately accounted for in the description of the SPEB thermodynamics. We anticipate that the present analysis, which provides possibly one of the first models for probing the electrostatics of pH-responsive SPEBs in a thermodynamically-consistent framework, will be vital for understanding the behavior of a large number of entities ranging from PE-coated NPs and stealth liposomes to biomolecules like bacteria and viruses. Copyright © 2016 Elsevier B.V. All rights reserved.

Controlled Supramolecular Self-Assembly of Super-charged β-Lactoglobulin A-PEG Conjugates into Nanocapsules.

PubMed

Khan, Amit Kumar; Gudlur, Sushanth; de Hoog, Hans-Peter M; Siti, Winna; Liedberg, Bo; Nallani, Madhavan

2017-09-18

The synthesis and characterization of a new protein-polymer conjugate composed of β lactoglobulin A (βLG A) and poly(ethylene glycol) PEG is described. βLG A was selectively modified to self-assemble by super-charging via amination or succinylation followed by conjugation with PEG. An equimolar mixture of the oppositely charged protein-polymer conjugates self-assemble into spherical capsules of 80-100 nm in diameter. The self-assembly proceeds by taking simultaneous advantage of the amphiphilicity and polyelectrolyte nature of the protein-polymer conjugate. These protein-polymer capsules or proteinosomes are reminiscent of protein capsids, and are capable of encapsulating solutes in their interior. We envisage this approach to be applicable to other globular proteins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stevens, Mark J.; Saleh, Omar A.

We calculated the force-extension curves for a flexible polyelectrolyte chain with varying charge separations by performing Monte Carlo simulations of a 5000 bead chain using a screened Coulomb interaction. At all charge separations, the force-extension curves exhibit a Pincus-like scaling regime at intermediate forces and a logarithmic regime at large forces. As the charge separation increases, the Pincus regime shifts to a larger range of forces and the logarithmic regime starts are larger forces. We also found that force-extension curve for the corresponding neutral chain has a logarithmic regime. Decreasing the diameter of bead in the neutral chain simulations removedmore » the logarithmic regime, and the force-extension curve tends to the freely jointed chain limit. In conclusion, this result shows that only excluded volume is required for the high force logarithmic regime to occur.« less

Release of DNA from polyelectrolyte multilayers fabricated using 'charge-shifting' cationic polymers: tunable temporal control and sequential, multi-agent release.

PubMed

Sun, Bin; Lynn, David M

2010-11-20

We report an approach to the design of multilayered polyelectrolyte thin films (or 'polyelectrolyte multilayers', PEMs) that can be used to provide tunable control over the release of plasmid DNA (or multiple different DNA constructs) from film-coated surfaces. Our approach is based upon methods for the layer-by-layer assembly of DNA-containing thin films, and exploits the properties of a new class of cationic 'charge-shifting' polymers (amine functionalized polymers that undergo gradual changes in net charge upon side chain ester hydrolysis) to provide control over the rates at which these films erode and release DNA. We synthesized two 'charge-shifting' polymers (polymers 1 and 2) containing different side chain structures by ring-opening reactions of poly(2-alkenyl azlactone)s with two different tertiary amine functionalized alcohols (3-dimethylamino-1-propanol and 2-dimethylaminoethanol, respectively). Subsequent characterization revealed large changes in the rates of side chain ester hydrolysis for these two polymers; whereas the half-life for the hydrolysis of the esters in polymer 1 was ~200 days, the half-life for polymer 2 was ~6 days. We demonstrate that these large differences in side chain hydrolysis make possible the design of PEMs that erode and promote the surface-mediated release of DNA either rapidly (e.g., over ~3 days for films fabricated using polymer 2) or slowly (e.g., over ~1 month for films fabricated using polymer 1). We demonstrate further that it is possible to design films with release profiles that are intermediate to these two extremes by fabricating films using solutions containing different mixtures of these two polymers. This approach can thus expand the usefulness of these two polymers and achieve a broader range of DNA release profiles without the need to synthesize polymers with new structures or properties. Finally, we demonstrate that polymers 1 and 2 can be used to fabricate multilayered films with hierarchical structures that promote the sequential release of two different DNA constructs with separate and distinct release profiles (e.g., the release of a first construct over a period of ~3 days, followed by the sustained release of a second for a period of ~70 days). With further development, this approach could contribute to the design of functional thin films and surface coatings that provide sophisticated control over the timing and the order of the release of two or more DNA constructs (or other agents) of interest in a range of biomedical contexts. Copyright © 2010 Elsevier B.V. All rights reserved.

Selective, ultrathin membrane skins prepared by deposition of novel polymer films on porous alumina supports

NASA Astrophysics Data System (ADS)

Balachandra, Anagi Manjula

Membrane-based separations are attractive in industrial processes because of their low energy costs and simple operation. However, low permeabilities often make membrane processes uneconomical. Since flux is inversely proportional to membrane thickness, composite membranes consisting of ultrathin, selective skins on highly permeable supports are required to simultaneously achieve high throughput and high selectivity. However, the synthesis of defect-free skins with thicknesses less than 50 nm is difficult, and thus flux is often limited. Layer-by-layer deposition of oppositely charged polyelectrolytes on porous supports is an attractive method to synthesize ultrathin ion-separation membranes with high flux and high selectivity. The ion-transport selectivity of multilayer polyelectrolyte membranes (MPMs) is primarily due to Donnan exclusion; therefore increase in fixed charge density should yield high selectivity. However, control over charge density in MPMs is difficult because charges on polycations are electrostatically compensated by charges on polyanions, and the net charge in the bulk of these films is small. To overcome this problem, we introduced a templating method to create ion-exchange sites in the bulk of the membrane. This strategy involves alternating deposition of a Cu2+-poly(acrylic acid) complex and poly(allylamine hydrochloride) on a porous alumina support followed by removal of Cu2+ and deprotonation to yield free -COO- ion-exchange sites. Diffusion dialysis studies showed that the Cl-/SO42-. Selectivity of Cu2+-templated membranes is 4-fold higher than that of membranes prepared in the absence of Cu2+. Post-deposition cross-linking of these membranes by heat-induced amide bond formation further increased Cl-/SO42- selectivity to values as high as 600. Room-temperature, surface-initiated atom transfer radical polymerization (ATRP) provides another convenient method for formation of ultrathin polymer skins. This process involves attachment of polymerization initiators to a porous alumina support and subsequent polymerization from these initiators. Because ATRP is a controlled polymerization technique, it yields well-defined polymer films with low polydispersity indices (narrow molecular weight distributions). Additionally, this method is attractive because film thickness can be easily controlled by adjusting polymerization time. Gas-permeability data showed that grafted poly(ethylene glycol dimethacrylate) membranes have a CO 2/CH4 selectivity of 20, whereas poly(2-hydroxyethyl methacrylate) (PHEMA) films grown from a surface have negligible selectivity. However, derivatization of PHEMA with pentadecafluorooctanoyl chloride increases the solubility of CO2 in the membrane and results in a CO2/CH4 selectivity of 9. Although composite PHEMA membranes have no significant gas-transport selectivity, diffusion dialysis studies with PHEMA membranes showed moderate ion-transport selectivities. Cross-linking of PHEMA membranes by reaction with succinyl chloride greatly enhanced anion-transport selectivities while maintaining reasonable flux. The selectivities of these systems demonstrate that alternating polyelectrolyte deposition and surface-initiated ATRP are indeed capable of forming ultrathin, defect-free membrane skins that can potentially be modified for specific separations.

Yield stress and scaling of polyelectrolyte multilayer modified suspensions: effect of polyelectrolyte conformation during multilayer assembly.

PubMed

Hess, Andreas; Aksel, Nuri

2013-09-10

The yield stress of polyelectrolyte multilayer modified suspensions exhibits a surprising dependence on the polyelectrolyte conformation of multilayer films. The rheological data scale onto a universal master curve for each polyelectrolyte conformation as the particle volume fraction, φ, and the ionic strength of the background fluid, I, are varied. It is shown that rough films with highly coiled, brushy polyelectrolytes significantly enhance the yield stress. Moreover, via the ionic strength I of the background fluid, the dynamic yield stress of brushy polyelectrolyte multilayers can be finely adjusted over 2 decades.

Pair interactions in polyelectrolyte-nanoparticle systems: Influence of dielectric inhomogeneities and the partial dissociation of polymers and nanoparticles.

PubMed

Pryamitsyn, Victor; Ganesan, Venkat

2015-10-28

We study the effective pair interactions between two charged spherical particles in polyelectrolyte solutions using polymer self-consistent field theory. In a recent study [V. Pryamitsyn and V. Ganesan, Macromolecules 47, 6095 (2015)], we considered a model in which the particles possess fixed charge density, the polymers contain a prespecified amount of dissociated charges and, the dielectric constant of the solution was assumed to be homogeneous in space and independent of the polymer concentration. In this article, we present results extending our earlier model to study situations in which either or both the particle and the polymers possess partially dissociable groups. Additionally, we also consider the case when the dielectric constant of the solution depends on the local concentration of the polymers and when the particle's dielectric constant is lower than that of the solvent. For each case, we quantify the polymer-mediated interactions between the particles as a function of the polymer concentrations and the degree of dissociation of the polymer and particles. Consistent with the results of our previous study, we observe that the polymer-mediated interparticle interactions consist of a short-range attraction and a long-range repulsion. The partial dissociablity of the polymer and particles was seen to have a strong influence on the strength of the repulsive portion of the interactions. Rendering the dielectric permittivity to be inhomogeneous has an even stronger effect on the repulsive interactions and results in changes to the qualitative nature of interactions in some parametric ranges.

Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions.

PubMed

Tagliazucchi, Mario; de la Cruz, Mónica Olvera; Szleifer, Igal

2010-03-23

The competition between chemical equilibrium, for example protonation, and physical interactions determines the molecular organization and functionality of biological and synthetic systems. Charge regulation by displacement of acid-base equilibrium induced by changes in the local environment provides a feedback mechanism that controls the balance between electrostatic, van der Waals, steric interactions and molecular organization. Which strategies do responsive systems follow to globally optimize chemical equilibrium and physical interactions? We address this question by theoretically studying model layers of end-grafted polyacids. These layers spontaneously form self-assembled aggregates, presenting domains of controlled local pH and whose morphologies can be manipulated by the composition of the solution in contact with the film. Charge regulation stabilizes micellar domains over a wide range of pH by reducing the local charge in the aggregate at the cost of chemical free energy and gaining in hydrophobic interactions. This balance determines the boundaries between different aggregate morphologies. We show that a qualitatively new form of organization arises from the coupling between physical interactions and protonation equilibrium. This optimization strategy presents itself with polyelectrolytes coexisting in two different and well-defined protonation states. Our results underline the need of considering the coupling between chemical equilibrium and physical interactions due to their highly nonadditive behavior. The predictions provide guidelines for the creation of responsive polymer layers presenting self-organized patterns with functional properties and they give insights for the understanding of competing interactions in highly inhomogeneous and constrained environments such as those relevant in nanotechnology and those responsible for biological cells function.

Bistability in Doped Organic Thin Film Transistors (Preprint)

DTIC Science & Technology

2007-03-01

small molecules (e.g. pentacene ). As such, they do not necessarily compete with these more typical organic transistors, but rather have pertinence...involves dipping a substrate between two dilute polyelectrolyte solutions of opposite charge to build up a thin film via the electrostatic interactions...recovery is due to trapped O2(g) remaining in the film, which causes the reverse of reaction (1) to occur and the concomitant increase in the level of

Effect of Pendant Side-Chain Sterics and Dipole Forces on Short Range Ordering in Random Polyelectrolytes

NASA Astrophysics Data System (ADS)

Nwosu, Chinomso; Pandey, Tara; Herring, Andrew; Coughlin, Edward; University of Massachusetts, Amherst Collaboration; Colorado School of Mines Collaboration

Backbone-to-backbone spacing in polymers is known to be dictated by the length of the pendant side-chains. Dipole forces in random polyelectrolytes lead to ionic clusters with a characteristic spacing that can be observed by SAXS. Repulsion due to side-chain sterics will compete with dipole forces driving cluster formation in random polyelectrolytes. A model study on short range order in anion exchange membranes (AEMs) of quaternized P4VP-ran-PI is presented. Quaternization of P4VP with alkyl bromides having different numbers of carbons, CnBr, introduces pendant side-chains as well as charges. X-ray scattering performed on PQ4VP-ran-PI(CnBr) show that when n <5 the dipole forces dominate leading to the formation of ionic clusters. However, when n >4, the chains remain separated due to sterics, forming a distinct backbone-to-backbone spacing morphology. For n=3, both dipole clustering and backbone spacing can coexist. Crosslinking of the isoprene units increased the coexistence window from n=3 to n=6. Impedance measurements show that a maximum conductivity of 110mS/cm was obtained for PQ4VP-ran-PI(C3Br). A discussion on short range order due to competition, or counter balancing, of steric repulsion and dipole forces will be presented. US Army MURI project (W911NF1010520).

Influence of Layer-by-Layer Polyelectrolyte Deposition and EDC/NHS Activated Heparin Immobilization onto Silk Fibroin Fabric

PubMed Central

Elahi, M. Fazley; Guan, Guoping; Wang, Lu; King, Martin W.

2014-01-01

To enhance the hemocompatibility of silk fibroin fabric as biomedical material, polyelectrolytes architectures have been assembled through the layer-by-layer (LbL) technique on silk fibroin fabric (SFF). In particular, 1.5 and 2.5 bilayer of oppositely charged polyelectrolytes were assembled onto SFF using poly(allylamine hydrochloride) (PAH) as polycationic polymer and poly(acrylic acid) (PAA) as polyanionic polymer with PAH topmost. Low molecular weight heparin (LMWH) activated with 1-ethyl-3-(dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) was then immobilized on its surface. Alcian Blue staining, toluidine blue assay and X-ray photoelectron spectroscopy (XPS) confirmed the presence of heparin on modified SFF surfaces. The surface morphology of the modified silk fibroin fabric surfaces was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), and obtained increased roughness. Negligible hemolytic effect and a higher concentration of free hemoglobin by a kinetic clotting time test ensured the improved biological performance of the modified fibroin fabric. Overall, the deposition of 2.5 bilayer was found effective in terms of biological and surface properties of the modified fibroin fabric compared to 1.5 bilayer self-assembly technique. Therefore, this novel approach to surface modification may demonstrate long term patency in future in vivo animal trials of small diameter silk fibroin vascular grafts. PMID:28788601

Effect of nanoparticles size and polyelectrolyte on nanoparticles aggregation in a cellulose fibrous matrix

DOE PAGES

Raghuwanshi, Vikram Singh; Garusinghe, Uthpala Manavi; Ilavsky, Jan; ...

2017-09-18

Controlling nanoparticles (NPs) aggregation in cellulose/NPs composites allows to optimise NPs driven properties and their applications. Polyelectrolytes are used to control NPs aggregation and their retention within the fibrous matrix. Here in this study, we aim at evaluating how a polyelectrolyte (Cationic Polyacrylamide; CPAM, molecular weight: 13 MDa, charge: 50%, Radius of gyration: 30–36 nm) adsorbs and re-conforms onto the surface of silica(SiO 2) NPs differing in diameter (8, 22 and 74 nm) and to investigate the respective NPs aggregation in cellulose matrices. SEM shows the local area distribution of NPs in composites. Ultra-SAXS (USAXS) allows to evaluate the averagemore » NPs size distribution and the inter-particle interactions at length scale ranging from 1 to 1000 nm. USAXS data analysis reveals that CPAM covers multiple NPs of the smaller diameter (8 nm), presumably with a single chain to form large size NPs aggregates. As the NPs diameter is increased to 22 nm, CPAM re-conforms over NP surface forming a large shell of thickness 5.5 nm. For the composites with NPs of diameter 74 nm, the CPAM chain re-conforms further onto NP surface and the surrounding shell thickness decreases to 2.2 nm. Lastly, structure factor analysis reveals higher structural ordering for NPs as increases their diameter, which is caused by different conformations adopted by CPAM onto NPs surface.« less

Electrokinetic energy conversion efficiency of viscoelastic fluids in a polyelectrolyte-grafted nanochannel.

PubMed

Jian, Yongjun; Li, Fengqin; Liu, Yongbo; Chang, Long; Liu, Quansheng; Yang, Liangui

2017-08-01

In order to conduct extensive investigation of energy harvesting capabilities of nanofluidic devices, we provide analytical solutions for streaming potential and electrokinetic energy conversion (EKEC) efficiency through taking the combined consequences of soft nanochannel, a rigid nanochannel whose surface is covered by charged polyelectrolyte layer, and viscoelastic rheology into account. The viscoelasticity of the fluid is considered by employing the Maxwell constitutive model when the forcing frequency of an oscillatory driving pressure flow matches with the inverse of the relaxation time scale of a typical viscoelastic fluid. We compare the streaming potential and EKEC efficiency with those of a rigid nanochannel, having zeta potential equal to the electrostatic potential at the solid-polyelectrolyte interface of the soft nanochannels. Within the present selected parameter ranges, it is shown that the different peaks of maximal streaming potential and EKEC efficiency for the rigid nanochannel are larger than those for the soft nanochannel when forcing frequencies of the driving pressure gradient are close to resonating frequencies. However, more enhanced streaming potential and EKEC efficiency for a soft nanochannel can be found in most of the regions away from these resonant frequencies. Moreover, the influence of several dimensionless parameters on EKEC efficiency is discussed in detail. Finally, within the given parametric regions, the maximum efficiency at some resonant frequency obtained in present analysis is about 25%. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of Salt Concentration on the pH Responses of Strong and Weak Polyelectrolyte Brushes.

PubMed

Zhang, Jian; Kou, Ran; Liu, Guangming

2017-07-11

Strong polyelectrolyte brushes (SPB) and weak polyelectrolyte brushes (WPB) have different origins with response to pH, which makes their pH-responsive properties sensitive to salt concentration in different ways. Herein, we have employed poly[2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC) and poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) brushes as model systems for SPB and WPB, respectively, to investigate the effect of salt concentration on the pH responses of SPB and WPB using several surface-sensitive techniques. The pH-responsive properties of the PMETAC brushes are governed by the reorganization of the interchain hydrogen bonds between the grafted chains, whereas the pH response of the PDMAEMA brushes is controlled by the charge of the grafted chains. The response of the properties of the PMETAC brushes including hydration, conformation, and surface wettability becomes weaker with increasing salt concentration induced by the competitive adsorption of counterions to the brushes between OH - and Cl - . The weakening of the pH response of the PMETAC brushes is more remarkable at the relatively high pH values. The pH response of the PDMAEMA brushes also exhibits a salt-concentration dependence. As the salt concentration increases, the weakening of the pH response of the PDMAEMA brushes is attributed to the decrease in osmotic pressure within the brushes at relatively low pH values.

Nanotemplated polyelectrolyte films as porous biomolecular delivery systems

PubMed Central

Gand, Adeline; Hindié, Mathilde; Chacon, Diane; van Tassel, Paul R; Pauthe, Emmanuel

2014-01-01

Biomaterials capable of delivering controlled quantities of bioactive agents, while maintaining mechanical integrity, are needed for a variety of cell contacting applications. We describe here a nanotemplating strategy toward porous, polyelectrolyte-based thin films capable of controlled biomolecular loading and release. Films are formed via the layer-by-layer assembly of charged polymers and nanoparticles (NP), then chemically cross-linked to increase mechanical rigidity and stability, and finally exposed to tetrahydrofuran to dissolve the NP and create an intra-film porous network. We report here on the loading and release of the growth factor bone morphogenetic protein 2 (BMP-2), and the influence of BMP-2 loaded films on contacting murine C2C12 myoblasts. We observe nanotemplating to enable stable BMP-2 loading throughout the thickness of the film, and find the nanotemplated film to exhibit comparable cell adhesion, and enhanced cell differentiation, compared with a non-porous cross-linked film (where BMP-2 loading is mainly confined to the film surface). PMID:25482416

Nanotemplated polyelectrolyte films as porous biomolecular delivery systems. Application to the growth factor BMP-2.

PubMed

Gand, Adeline; Hindié, Mathilde; Chacon, Diane; Van Tassel, Paul R; Pauthe, Emmanuel

2014-01-01

Biomaterials capable of delivering controlled quantities of bioactive agents, while maintaining mechanical integrity, are needed for a variety of cell contacting applications. We describe here a nanotemplating strategy toward porous, polyelectrolyte-based thin films capable of controlled biomolecular loading and release. Films are formed via the layer-by-layer assembly of charged polymers and nanoparticles (NP), then chemically cross-linked to increase mechanical rigidity and stability, and finally exposed to tetrahydrofuran to dissolve the NP and create an intra-film porous network. We report here on the loading and release of the growth factor bone morphogenetic protein 2 (BMP-2), and the influence of BMP-2 loaded films on contacting murine C2C12 myoblasts. We observe nanotemplating to enable stable BMP-2 loading throughout the thickness of the film, and find the nanotemplated film to exhibit comparable cell adhesion, and enhanced cell differentiation, compared with a non-porous cross-linked film (where BMP-2 loading is mainly confined to the film surface).

Smart electronic yarns and wearable fabrics for human biomonitoring made by carbon nanotube coating with polyelectrolytes.

PubMed

Shim, Bong Sup; Chen, Wei; Doty, Chris; Xu, Chuanlai; Kotov, Nicholas A

2008-12-01

The idea of electronic yarns and textiles has appeared for quite some time, but their properties often do not meet practical expectations. In addition to chemicallmechanical durability and high electrical conductivity, important materials qualifications include weavablity, wearability, light weight, and "smart" functionalities. Here we demonstrate a simple process of transforming general commodity cotton threads into intelligent e-textiles using a polyelectrolyte-based coating with carbon nanotubes (CNTs). Efficient charge transport through the network of nanotubes (20 omega/cm) and the possibility to engineer tunneling junctions make them promising materials for many high-knowledge-content garments. Along with integrated humidity sensing, we demonstrate that CNT-cotton threads can be used to detect albumin, the key protein of blood, with high sensitivity and selectivity. Notwithstanding future challenges, these proof-of-concept demonstrations provide a direct pathway for the application of these materials as wearable biomonitoring and telemedicine sensors, which are simple, sensitive, selective, and versatile.

Equilibration of a polycation - anionic surfactant mixture at the water/vapor interface.

PubMed

Akanno, Andrew; Guzmán, Eduardo; Fernández-Peña, Laura; Llamas, Sara; Ortega, Francisco; Rubio, Ramon Gonzalez

2018-06-01

The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC) - sodium lauryl ether sulfate (SLES) mixtures at the water / vapor interface has been studied by different surface tension techniques and dilational visco-elasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte - surfactant complexes in the bulk affects to the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC - SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work helps on the understanding of the most fundamental bases of the physico-chemical behavior of concentrated polyelectrolyte - surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

PubMed

Xu, Weinan; Ledin, Petr A; Shevchenko, Valery V; Tsukruk, Vladimir V

2015-06-17

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

Theory of polyelectrolytes in solvents.

PubMed

Chitanvis, Shirish M

2003-12-01

Using a continuum description, we account for fluctuations in the ionic solvent surrounding a Gaussian, charged chain and derive an effective short-ranged potential between the charges on the chain. This potential is repulsive at short separations and attractive at longer distances. The chemical potential can be derived from this potential. When the chemical potential is positive, it leads to a meltlike state. For a vanishingly low concentration of segments, this state exhibits scaling behavior for long chains. The Flory exponent characterizing the radius of gyration for long chains is calculated to be approximately 0.63, close to the classical value obtained for second order phase transitions. For short chains, the radius of gyration varies linearly with N, the chain length, and is sensitive to the parameters in the interaction potential. The linear dependence on the chain length N indicates a stiff behavior. The chemical potential associated with this interaction changes sign, when the screening length in the ionic solvent exceeds a critical value. This leads to condensation when the chemical potential is negative. In this state, it is shown using the mean-field approximation that spherical and toroidal condensed shapes can be obtained. The thickness of the toroidal polyelectrolyte is studied as a function of the parameters of the model, such as the ionic screening length. The predictions of this theory should be amenable to experimental verification.

The role of poly(methacrylic acid) conformation on dispersion behavior of nano TiO2 powder

NASA Astrophysics Data System (ADS)

Singh, Bimal P.; Nayak, Sasmita; Samal, Samata; Bhattacharjee, Sarama; Besra, Laxmidhar

2012-02-01

To exploit the advantages of nanoparticles for various applications, controlling the dispersion and agglomeration is of paramount importance. Agglomeration and dispersion behavior of titanium dioxide (TiO2) nanoparticles was investigated using electrokinetic and surface chemical properties. Nanoparticles are generally stabilized by the adsorption of a dispersant (polyelectrolyte) layer around the particle surface and in this connection ammonium salt of polymethacrylic acid (Darvan C) was used as dispersant to stabilize the suspension. The dosages of polyelectrolyte were optimized to get best dispersion stability by techniques namely particle charge detector (13.75 mg/g) and adsorption (14.57 mg/g). The surface charge of TiO2 particles changed significantly in presence of dispersant Darvan C and isoelectric point (iep) shifted significantly towards lower pH from 5.99 to 3.37. The shift in iep has been quantified in terms of free energy of interaction between the surface sites of TiO2 and the adsorbing dispersant Darvan C. Free energies of adsorption were calculated by electrokinetic data (-9.8 RT unit) and adsorption isotherms (-10.56 RT unit), which corroborated well. The adsorption isotherms are of typical Langmuir type and employed for calculation of free energy. The results indicated that adsorption occurs mainly through electrostatic interactions between the dispersant molecule and the TiO2 surface apart from hydrophobic interactions.

Single-coil properties and concentration effects for polyelectrolyte-like wormlike micelles: a Monte Carlo study

NASA Astrophysics Data System (ADS)

Cannavacciuolo, Luigi; Skov Pedersen, Jan; Schurtenberger, Peter

2002-03-01

Results of an extensive Monte Carlo (MC) study on both single and many semiflexible charged chains with excluded volume (EV) are summarized. The model employed has been tailored to mimic wormlike micelles in solution. Simulations have been performed at different ionic strengths of added salt, charge densities, chain lengths and volume fractions Φ, covering the dilute to concentrated regime. At infinite dilution the scattering functions can be fitted by the same fitting functions as for uncharged semiflexible chains with EV, provided that an electrostatic contribution bel is added to the bare Kuhn length. The scaling of bel is found to be more complex than the Odijk-Skolnick-Fixman predictions, and qualitatively compatible with more recent variational calculations. Universality in the scaling of the radius of gyration is found if all lengths are rescaled by the total Kuhn length. At finite concentrations, the simple model used is able to reproduce the structural peak in the scattering function S(q) observed in many experiments, as well as other properties of polyelectrolytes (PELs) in solution. Universal behaviour of the forward scattering S(0) is established after a rescaling of Φ. MC data are found to be in very good agreement with experimental scattering measurements with equilibrium PELs, which are giant wormlike micelles formed in mixtures of nonionic and ionic surfactants in dilute aqueous solution, with added salt.

Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation

NASA Astrophysics Data System (ADS)

Malekzadeh Moghani, Mahdy; Khomami, Bamin

2016-01-01

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ˜ cs-0.5 as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation.

PubMed

Malekzadeh Moghani, Mahdy; Khomami, Bamin

2016-01-14

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ∼ cs (-0.5) as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

Electrostatic Forces as Dominant Interactions Between Proteins and Polyanions: an ESI MS Study of Fibroblast Growth Factor Binding to Heparin Oligomers

NASA Astrophysics Data System (ADS)

Minsky, Burcu Baykal; Dubin, Paul L.; Kaltashov, Igor A.

2017-04-01

The interactions between fibroblast growth factors (FGFs) and their receptors (FGFRs) are facilitated by heparan sulfate (HS) and heparin (Hp), highly sulfated biological polyelectrolytes. The molecular basis of FGF interactions with these polyelectrolytes is highly complex due to the structural heterogeneity of HS/Hp, and many details still remain elusive, especially the significance of charge density and minimal chain length of HS/Hp in growth factor recognition and multimerization. In this work, we use electrospray ionization mass spectrometry (ESI MS) to investigate the association of relatively homogeneous oligoheparins (octamer, dp8, and decamer, dp10) with acidic fibroblast growth factor (FGF-1). This growth factor forms 1:1, 2:1, and 3:1 protein/heparinoid complexes with both dp8 and dp10, and the fraction of bound protein is highly dependent on protein/heparinoid molar ratio. Multimeric complexes are preferentially formed on the highly sulfated Hp oligomers. Although a variety of oligomers appear to be binding-competent, there is a strong correlation between the affinity and the overall level of sulfation (the highest charge density polyanions binding FGF most strongly via multivalent interactions). These results show that the interactions between FGF-1 and Hp oligomers are primarily directed by electrostatics, and also demonstrate the power of ESI MS as a tool to study multiple binding equilibria between proteins and structurally heterogeneous polyanions.

Label-free detection of DNA using a light-addressable potentiometric sensor modified with a positively charged polyelectrolyte layer

NASA Astrophysics Data System (ADS)

Wu, Chunsheng; Bronder, Thomas; Poghossian, Arshak; Werner, Carl Frederik; Schöning, Michael J.

2015-03-01

A multi-spot (16 spots) light-addressable potentiometric sensor (MLAPS) consisting of an Al-p-Si-SiO2 structure modified with a weak polyelectrolyte layer of PAH (poly(allylamine hydrochloride)) was applied for the label-free electrical detection of DNA (deoxyribonucleic acid) immobilization and hybridization by the intrinsic molecular charge for the first time. To achieve a preferentially flat orientation of DNA strands and thus, to reduce the distance between the DNA charge and MLAPS surface, the negatively charged probe single-stranded DNAs (ssDNA) were electrostatically adsorbed onto the positively charged PAH layer using a simple layer-by-layer (LbL) technique. In this way, more DNA charge can be positioned within the Debye length, yielding a higher sensor signal. The surface potential changes in each spot induced due to the surface modification steps (PAH adsorption, probe ssDNA immobilization, hybridization with complementary target DNA (cDNA), non-specific adsorption of mismatched ssDNA) were determined from the shifts of photocurrent-voltage curves along the voltage axis. A high sensor signal of 83 mV was registered after immobilization of probe ssDNA onto the PAH layer. The hybridization signal increases from 5 mV to 32 mV with increasing the concentration of cDNA from 0.1 nM to 5 μM. In contrast, a small signal of 5 mV was recorded in the case of non-specific adsorption of fully mismatched ssDNA (5 μM). The obtained results demonstrate the potential of the MLAPS in combination with the simple and rapid LbL immobilization technique as a promising platform for the future development of multi-spot light-addressable label-free DNA chips with direct electrical readout.A multi-spot (16 spots) light-addressable potentiometric sensor (MLAPS) consisting of an Al-p-Si-SiO2 structure modified with a weak polyelectrolyte layer of PAH (poly(allylamine hydrochloride)) was applied for the label-free electrical detection of DNA (deoxyribonucleic acid) immobilization and hybridization by the intrinsic molecular charge for the first time. To achieve a preferentially flat orientation of DNA strands and thus, to reduce the distance between the DNA charge and MLAPS surface, the negatively charged probe single-stranded DNAs (ssDNA) were electrostatically adsorbed onto the positively charged PAH layer using a simple layer-by-layer (LbL) technique. In this way, more DNA charge can be positioned within the Debye length, yielding a higher sensor signal. The surface potential changes in each spot induced due to the surface modification steps (PAH adsorption, probe ssDNA immobilization, hybridization with complementary target DNA (cDNA), non-specific adsorption of mismatched ssDNA) were determined from the shifts of photocurrent-voltage curves along the voltage axis. A high sensor signal of 83 mV was registered after immobilization of probe ssDNA onto the PAH layer. The hybridization signal increases from 5 mV to 32 mV with increasing the concentration of cDNA from 0.1 nM to 5 μM. In contrast, a small signal of 5 mV was recorded in the case of non-specific adsorption of fully mismatched ssDNA (5 μM). The obtained results demonstrate the potential of the MLAPS in combination with the simple and rapid LbL immobilization technique as a promising platform for the future development of multi-spot light-addressable label-free DNA chips with direct electrical readout. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07225a

Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers

NASA Astrophysics Data System (ADS)

White, Nicholas

Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is <2. However, water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains high salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000 because the diffusion-limited K+ or Li+ currents exceed the applied current. However, ED selectivities gradually decline with time. Thus, future research should aim to increase membrane stability and limiting currents to fully exploit the remarkable selectivity of these membranes. PEMs deposited on commercial ultrafiltration (UF) membranes also show high rejections of organic dyes. Coating the surface of polyethersulfone (PES) membranes imparts a selective barrier to dye molecules used in textile production. These films achieve dye rejections >98% and may be useful for wastewater treatment and dye recovery. Other studies in microfluidic channels exploit ion transport phenomena in the vicinity of ion-selective junctions, such as cation-exchange membranes. These studies suggest that ion concentration polarization (ICP) could remove charged species from feed streams.

Directed assembly of three-dimensional structures with micron-scale features

DOEpatents

Gratson, Gregory; Lewis, Jennifer A.

2006-11-28

The invention provides polyelectrolyte inks comprising a solvent, a cationic polyelectrolyte, dissolved in the solvent, and an anionic polyelectrolyte, dissolved in the solvent. The concentration of at least one of the polyelectrolytes in the solvent is in a semidilute regime.

Adsorption of human serum albumin: Dependence on molecular architecture of the oppositely charged surface

NASA Astrophysics Data System (ADS)

Sukhishvili, Svetlana A.; Granick, Steve

1999-05-01

We contrast the adsorption of human serum albumin (HSA) onto two solid substrates previously primed with the same polyelectrolyte of net opposite charge to form one of two alternative structures: randomly adsorbed polymer and the "brush" configuration. These structures were formed either by the adsorption of quaternized poly-4-vinylpyridine (QPVP) or by end-grafting QPVP chains of the same chemical makeup and the same molecular weight to surfaces onto which QPVP segments did not adsorb. The adsorption of HSA was quantified by using Fourier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR). The two substrates showed striking differences with regard to HSA adsorption. First, the brush substrate induced lesser perturbations in the secondary structure of the adsorbed HSA, reflecting easier conformational adjustment for longer free segments of polyelectrolyte upon binding with the protein. Second, the penetration of HSA into the brush substrate was kinetically retarded relative to the randomly adsorbed polymer, probably due to both pore size restriction and electrostatic sticking between charged groups of HSA and QPVP molecules. Third, release of HSA from the adsorbed layer, as the ionic strength was increased from a low level up to the high level of 1 M NaCl, was largely inhibited for the brush substrate, but occurred easily and rapidly for the substrate with statistically adsorbed QPVP chains. Finally, even after addition of a strong polymeric adsorption competitor (sodium polystyrene sulfonate), HSA remained trapped within a brush substrate though it desorbed slowly from the preadsorbed QPVP layer. This method to produce irreversible trapping of the protein within a brush substrate without major conformational change may find application in biosensor design.

An ionic-chemical-mechanical model for muscle contraction.

PubMed

Manning, Gerald S

2016-12-01

The dynamic process underlying muscle contraction is the parallel sliding of thin actin filaments along an immobile thick myosin fiber powered by oar-like movements of protruding myosin cross bridges (myosin heads). The free energy for functioning of the myosin nanomotor comes from the hydrolysis of ATP bound to the myosin heads. The unit step of translational movement is based on a mechanical-chemical cycle involving ATP binding to myosin, hydrolysis of the bound ATP with ultimate release of the hydrolysis products, stress-generating conformational changes in the myosin cross bridge, and relief of built-up stress in the myosin power stroke. The cycle is regulated by a transition between weak and strong actin-myosin binding affinities. The dissociation of the weakly bound complex by addition of salt indicates the electrostatic basis for the weak affinity, while structural studies demonstrate that electrostatic interactions among negatively charged amino acid residues of actin and positively charged residues of myosin are involved in the strong binding interface. We therefore conjecture that intermediate states of increasing actin-myosin engagement during the weak-to-strong binding transition also involve electrostatic interactions. Methods of polymer solution physics have shown that the thin actin filament can be regarded in some of its aspects as a net negatively charged polyelectrolyte. Here we employ polyelectrolyte theory to suggest how actin-myosin electrostatic interactions might be of significance in the intermediate stages of binding, ensuring an engaged power stroke of the myosin motor that transmits force to the actin filament, and preventing the motor from getting stuck in a metastable pre-power stroke state. We provide electrostatic force estimates that are in the pN range known to operate in the cycle. © 2016 Wiley Periodicals, Inc.

A PDDA/poly(2,6-pyridinedicarboxylic acid)-CNTs composite film DNA electrochemical sensor and its application for the detection of specific sequences related to PAT gene and NOS gene.

PubMed

Yang, Tao; Zhang, Wei; Du, Meng; Jiao, Kui

2008-05-30

2,6-Pyridinedicarboxylic acid (PDC) was electropolymerized on the glassy carbon electrode (GCE) surface combined with carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) by cyclic voltammetry (CV) to form PDC-SWNTs composite film, which was rich in negatively charged carboxylic group. Then, poly(diallyldimethyl ammonium chloride) (PDDA), a linear cationic polyelectrolyte, was electrostatically adsorbed on the PDC-SWNTs/GCE surface. DNA probes with negatively charged phosphate group at the 5' end were immobilized on the PDDA/PDC-SWNTs/GCE due to the strong electrostatic attraction between PDDA and phosphate group of DNA. It has been found that modification of the electrode with PDC-SWNTs film has enhanced the effective electrode surface area and electron-transfer ability, in addition to providing negatively charged groups for the electrostatic assembly of cationic polyelectrolyte. PDDA plays a key role in the attachment of DNA probes to the PDC-SWNTs composite film and acts as a bridge to connect DNA with PDC-SWNTs film. The cathodic peak current of methylene blue (MB), an electroactive label, decreased obviously after the hybridization of DNA probe (ssDNA) with the complementary DNA (cDNA). This peak current change was used to monitor the recognition of the specific sequences related to PAT gene in the transgenic corn and the polymerase chain reaction (PCR) amplification of NOS gene from the sample of transgenic soybean with satisfactory results. Under optimal conditions, the dynamic detection range of the sensor to PAT gene target sequence was from 1.0x10(-11) to 1.0x10(-6) mol/L with the detection limit of 2.6x10(-12) mol/L.

Dynamic swelling of tunable full-color block copolymer photonic gels via counterion exchange.

PubMed

Lim, Ho Sun; Lee, Jae-Hwang; Walish, Joseph J; Thomas, Edwin L

2012-10-23

One-dimensionally periodic block copolymer photonic lamellar gels with full-color tunability as a result of a direct exchange of counteranions were fabricated via a two-step procedure comprising the self-assembly of a hydrophobic block-hydrophilic polyelectrolyte block copolymer, polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP), followed by sequential quaternization of the P2VP layers in 1-bromoethane solution. Depending on the hydration characteristics of each counteranion, the selective swelling of the block copolymer lamellar structures leads to large tunability of the photonic stop band from blue to red wavelengths. More extensive quaternization of the P2VP block allows the photonic lamellar gels to swell more and red shift to longer wavelength. Here, we investigate the dynamic swelling behavior in the photonic gel films through time-resolved in situ measurement of UV-vis transmission. We model the swelling behavior using the transfer matrix method based on the experimentally observed reflectivity data with substitution of appropriate counterions. These tunable structural color materials may be attractive for numerous applications such as high-contrast displays without using a backlight, color filters, and optical mirrors for flexible lasing.

Salt- and pH-induced desorption: Comparison between non-aggregated and aggregated mussel adhesive protein, Mefp-1, and a synthetic cationic polyelectrolyte.

PubMed

Krivosheeva, Olga; Dedinaite, Andra; Claesson, Per M

2013-10-15

Mussel adhesive proteins are of great interest in many applications due to their ability to bind strongly to many types of surfaces under water. Effective use such proteins, for instance the Mytilus edulis foot protein - Mefp-1, for surface modification requires achievement of a large adsorbed amount and formation of a layer that is resistant towards desorption under changing conditions. In this work we compare the adsorbed amount and layer properties obtained by using a sample containing small Mefp-1 aggregates with that obtained by using a non-aggregated sample. We find that the use of the sample containing small aggregates leads to higher adsorbed amount, larger layer thickness and similar water content compared to what can be achieved with a non-aggregated sample. The layer formed by the aggregated Mefp-1 was, after removal of the protein from bulk solution, exposed to aqueous solutions with high ionic strength (up to 1M NaCl) and to solutions with low pH in order to reduce the electrostatic surface affinity. It was found that the preadsorbed Mefp-1 layer under all conditions explored was significantly more resistant towards desorption than a layer built by a synthetic cationic polyelectrolyte with similar charge density. These results suggest that the non-electrostatic surface affinity for Mefp-1 is larger than for the cationic polyelectrolyte. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

Confined polyelectrolytes: The complexity of a simple system.

PubMed

Nunes, Sandra C C; Skepö, Marie; Pais, Alberto A C C

2015-08-05

The interaction between polyelectrolytes and counterions in confined situations and the mutual relationship between chain conformation and ion condensation is an important issue in several areas. In the biological field, it assumes particular relevance in the understanding of the packaging of nucleic acids, which is crucial in the design of gene delivery systems. In this work, a simple coarse-grained model is used to assess the cooperativity between conformational change and ion condensation in spherically confined backbones, with capsides permeable to the counterions. It is seen that the variation on the degree of condensation depends on counterion valence. For monovalent counterions, the degree of condensation passes through a minimum before increasing as the confining space diminishes. In contrast, for trivalent ions, the overall tendency is to decrease the degree of condensation as the confinement space also decreases. Most of the particles reside close to the spherical wall, even for systems in which the density is higher closer to the cavity center. This effect is more pronounced, when monovalent counterions are present. Additionally, there are clear variations in the charge along the concentric layers that cannot be totally ascribed to polyelectrolyte behavior, as shown by decoupling the chain into monomers. If both chain and counterions are confined, the formation of a counterion rich region immediately before the wall is observed. Spool and doughnut-like structures are formed for stiff chains, within a nontrivial evolution with increasing confinement. © 2015 Wiley Periodicals, Inc.

On the mesoscopic origins of high viscosities in some polyelectrolyte-surfactant mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, Ingo, E-mail: ingo.hoffmann@tu-berlin.de; Institut Max von Laue-Paul Langevin; Farago, Bela

Oppositely charged polyelectrolyte (PE) surfactant mixtures allow the control of rheological parameters of a solution even at fairly low concentrations. For example, addition of 0.3 wt. % of anionic surfactant to a 1 wt. % solution of the polycation JR 400 increases the viscosity by 4 orders of magnitude. Recently, we could show that this increase is related to the formation of mixed, rod-like PE/surfactant aggregates which interconnect several polyelectrolyte chains [Hoffmann et al., Europhys. Lett. 104, 28001 (2013)]. In this paper, we refine our structural model of the aggregates to obtain a more consistent picture of their internal structure for differentmore » anionic surfactants. Combining small angle neutron scattering (SANS) and neutron spin-echo (NSE) allows us to determine the size of the aggregates. By comparing different contrasts, the internal structure of the aggregates can be elucidated and it is seen that the PE in the aggregates retains a relatively high freedom of movement. We proceeded to investigate the influence of the surfactant concentration and the surfactant type on structure and dynamics of the mixed aggregates. It is seen that the structural parameters of the aggregates depend very little on the surfactant concentration and headgroup. However, it is crucial to incorporate a sufficient amount of PE in the aggregates to increase the viscosity of the aggregates. By comparing viscous samples at 1 wt. % PE concentration with samples at a PE concentration of 0.3 wt. %, where no significant increase in viscosity is observed, we find that similar aggregates are formed already at this lower PE concentrations. However, the amount of PE incorporated in them is insufficient to interconnect several PE chains and therefore, they do not increase viscosity. So, our detailed investigation combining contrast variation SANS and NSE does not only allow to explain the viscosity behavior but also to deduced detailed information regarding the structures and the dynamics especially of the polyelectrolyte within the complexes.« less

Imatinib-loaded polyelectrolyte microcapsules for sustained targeting of BCR-ABL+ leukemia stem cells.

PubMed

Palamà, Ilaria E; Leporatti, Stefano; de Luca, Emanuela; Di Renzo, Nicola; Maffia, Michele; Gambacorti-Passerini, Carlo; Rinaldi, Ross; Gigli, Giuseppe; Cingolani, Roberto; Coluccia, Addolorata M L

2010-04-01

The lack of sensitivity of chronic myeloid leukemia (CML) stem cells to imatinib mesylate (IM) commonly leads to drug dose escalation or early disease relapses when therapy is stopped. Here, we report that packaging of IM into a biodegradable carrier based on polyelectrolyte microcapsules increases drug retention and antitumor activity in CML stem cells, also improving the ex vivo purging of malignant progenitors from patient autografts. Microparticles/capsules were obtained by layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolyte multilayers on removable calcium carbonate (CaCO(3)) templates and loaded with or without IM. A leukemic cell line (KU812) and CD34(+) cells freshly isolated from healthy donors or CML patients were tested. Polyelectrolyte microcapsules (PMCs) with an average diameter of 3 microm, fluorescently labelled multilayers sensitive to the action of intracellular proteases and 95-99% encapsulation efficiency of IM, were prepared. Cell uptake efficiency of such biodegradable carriers was quantified in KU812, leukemic and normal CD34(+) stem cells (range: 70-85%), and empty PMCs did not impact cell viability. IM-loaded PMCs selectively targeted CML cells, by promoting apoptosis at doses that exert only cytostatic effects by IM alone. More importantly, residual CML cells from patient leukapheresis products were reduced or eliminated more efficiently by using IM-loaded PMCs compared with freely soluble IM, with a purging efficiency of several logs. No adverse effects on normal CD34(+) stem-cell survival and their clonogenic potential was noticed in long-term cultures of hematopoietic progenitors in vitro. This pilot study provides the proof-of-principle for the clinical application of biodegradable IM-loaded PMC as feasible, safe and effective ex vivo purging agents to target CML stem cells, in order to improve transplant outcome of resistant/relapsed patients or reduce IM dose escalation.

Adsorption and flocculation by polymers and polymer mixtures.

PubMed

Gregory, John; Barany, Sandor

2011-11-14

Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including 'electrostatic patch' attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of 'site blocking'. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrical Oscillations in Two-Dimensional Microtubular Structures

PubMed Central

Cantero, María del Rocío; Perez, Paula L.; Smoler, Mariano; Villa Etchegoyen, Cecilia; Cantiello, Horacio F.

2016-01-01

Microtubules (MTs) are unique components of the cytoskeleton formed by hollow cylindrical structures of αβ tubulin dimeric units. The structural wall of the MT is interspersed by nanopores formed by the lateral arrangement of its subunits. MTs are also highly charged polar polyelectrolytes, capable of amplifying electrical signals. The actual nature of these electrodynamic capabilities remains largely unknown. Herein we applied the patch clamp technique to two-dimensional MT sheets, to characterize their electrical properties. Voltage-clamped MT sheets generated cation-selective oscillatory electrical currents whose magnitude depended on both the holding potential, and ionic strength and composition. The oscillations progressed through various modes including single and double periodic regimes and more complex behaviours, being prominent a fundamental frequency at 29 Hz. In physiological K+ (140 mM), oscillations represented in average a 640% change in conductance that was also affected by the prevalent anion. Current injection induced voltage oscillations, thus showing excitability akin with action potentials. The electrical oscillations were entirely blocked by taxol, with pseudo Michaelis-Menten kinetics and a KD of ~1.29 μM. The findings suggest a functional role of the nanopores in the MT wall on the genesis of electrical oscillations that offer new insights into the nonlinear behaviour of the cytoskeleton. PMID:27256791

Preparation of K+-Doped Core-Shell NaYF4:Yb, Er Upconversion Nanoparticles and its Application for Fluorescence Immunochromatographic Assay of Human Procalcitonin.

PubMed

Tang, Jie; Lei, Lijiang; Feng, Hui; Zhang, Hongman; Han, Yuwang

2016-11-01

In the present study, we reported a convenient route to prepare well dispersed and functionalized K + -doped core-shell upconversion nanoparticles (UCP) by layer-by-layer (LbL) assembly of polyelectrolytes. UCP was firstly transferred to aqueous phase using cationic surfactant cetyl trimethyl ammonium bromide (CTAB) via hydrophobic interaction without removing the existing oleic acid (OA). Then the positively charged hydrophilic UCP@CTAB was further alternately deposited with negatively charged [poly (sodium 4-styrenesulfonate)] (PSS), positively charged [poly (allylamine hydrochloride)] (PAH) and negatively charged [poly (acrylic acid)] (PAA). The final carboxyl functionalized UCP@CTAB@PSS@PAH@PAA was then conjugated with monoclonal antibody1 (AB1) of procalcitonin (PCT), resulting in successful detection of PCT antigens based on the immunochromatographic assay (ICA). Linear response was achieved from 0 to 10 ng/mL, and the lowest limit of detection (LLD) was 0.18 ng/mL.

Design of asymmetric particles containing a charged interior and a neutral surface charge: comparative study on in vivo circulation of polyelectrolyte microgels.

PubMed

Chen, Kai; Xu, Jing; Luft, J Christopher; Tian, Shaomin; Raval, Jay S; DeSimone, Joseph M

2014-07-16

Lowering the modulus of hydrogel particles could enable them to bypass in vivo physical barriers that would otherwise filter particles with similar size but higher modulus. Incorporation of electrolyte moieties into the polymer network of hydrogel particles to increase the swelling ratio is a straightforward and quite efficient way to decrease the modulus. In addition, charged groups in hydrogel particles can also help secure cargoes. However, the distribution of charged groups on the surface of a particle can accelerate the clearance of particles. Herein, we developed a method to synthesize highly swollen microgels of precise size with near-neutral surface charge while retaining interior charged groups. A strategy was employed to enable a particle to be highly cross-linked with very small mesh size, and subsequently PEGylated to quench the exterior amines only without affecting the internal amines. Acidic degradation of the cross-linker allows for swelling of the particles to microgels with a desired size and deformability. The microgels fabricated demonstrated extended circulation in vivo compared to their counterparts with a charged surface, and could potentially be utilized in in vivo applications including as oxygen carriers or nucleic acid scavengers.

Colloidal titration of aqueous zirconium solutions with poly(vinyl sulfate) by potentiometric endpoint detection using a toluidine blue selective electrode.

PubMed

Sakurada, Osamu; Kato, Yasutake; Kito, Noriyoshi; Kameyama, Keiichi; Hattori, Toshiaki; Hashiba, Minoru

2004-02-01

Zirconium oxy-salts were hydrolyzed to form positively charged polymer or cluster species in acidic solutions. The zirconium hydrolyzed polymer was found to react with a negatively charged polyelectrolyte, such as poly(vinyl sulfate), and to form a stoichiometric polyion complex. Thus, colloidal titration with poly(vinyl sulfate) was applied to measure the zirconium concentration in an acidic solution by using a Toluidine Blue selective plasticized poly(vinyl chloride) membrane electrode as a potentiometric end-point detecting device. The determination could be performed with 1% of the relative standard deviation. The colloidal titration stoichiometry at pH < or = 2 was one mol of zirconium per equivalent mol of poly(vinyl sulfate).

Deposition of zeolite nanoparticles onto porous silica monolith

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gackowski, Mariusz; Bielanska, Elzbieta; Szczepanowicz, Krzysztof

2016-06-01

A facile and effective method of deposition of MFl zeolite nanoparticles (nanocrystals) onto macro-/mesoporous silica monolith was proposed. The electrostatic interaction between those two materials was induces by adsorption of cationic polyelectrolytes. That can be realized either by adsorption of polyelectrolyte onto silica monolith or on zeolite nanocrystals. The effect of time, concentration of zeolite nanocrystals, type of polyelectrolyte, and ultrasound treatment is scrutinized. Adsorption of polyelectrolyte onto silica monolith with subsequent deposition of nanocrystals resulted in a monolayer coverage assessed with SEM images. Infrared spectroscopy was applied as a useful method to determine the deposition effectiveness of zeolite nanocrystalsmore » onto silica. Modification of nanocrystals with polyelectrolyte resulted in a multilayer coverage due to agglomeration of particles. On the other hand, the excess of polyelectrolyte in the system resulted in a low coverage due to competition between polyelectrolyte and modified nanocrystals.« less

Measurement and Control of Electroosmotic Flow in Plastic Microchannels

NASA Astrophysics Data System (ADS)

Ross, David; Barker, Susan; Waddell, Emanuel; Johnson, Tim; Locascio, Laurie

2000-11-01

We have measured electroosmotic flow profiles in microchannels fabricated in a variety of commercially available plastics by imprinting using a silicon template and by UV laser ablation. It is possible to achieve nearly ideal plug flow profiles in straight imprinted channels made entirely of one material. In contrast, electroosmotic flow in imprinted channels constructed from two different materials and in channels fabricated using laser ablation show deviations from ideal plug flow resulting from non-uniformity of the surface charge density on the walls of the channels. We have also explored strategies for controlling electroosmotic flow through modification of the surface charge density. The techniques used to alter surface charge include the deposition of polyelectrolyte multilayers on channel surfaces and the use of combinations of imprinting and laser ablation in the fabrication of the channels. We will discuss the effectiveness of these strategies for controlling flow, sample dispersion, and mixing.

Picosecond absorption studies of photoinduced charge separation in polyelectrolyte bound aromatic chromophores

NASA Astrophysics Data System (ADS)

Shand, M. A.; Rodgers, M. A. J.; Webber, S. E.

1991-02-01

Picosecond absorption studies of photoinduced electron transfer between aromatic chromophores bound to polymethacrylic acid (P) and methylviologen (MV 2+ have been carried out in aqueous solution. The diphenylanthracene copolymer/viologen system at pH 2.8 shows the corresponding redox products DPA + rad and MV + rad arising from the singlet state of DPA with a forward rate constant of electron transfer of 2.6 × 10 9 s -1. At pH 9.0 the quenching of the S 1 state of DPA occurs with no charge separated products being observed. The pyrene copolymer shows no evidence of charge separated products at any pH in the range 2.8-9.0. It is proposed that the differences in the radical pair kinetics arise from differences in the degree of binding of the ground state complexes formed by the donor and acceptor species.

Reversible modulation of the redox activity in conducting polymer nanofilms induced by hydrophobic collapse of a surface-grafted polyelectrolyte.

PubMed

Fenoy, Gonzalo E; Giussi, Juan M; von Bilderling, Catalina; Maza, Eliana M; Pietrasanta, Lía I; Knoll, Wolfgang; Marmisollé, Waldemar A; Azzaroni, Omar

2018-05-15

We present the covalent modification of a Pani-like conducting polymer (polyaminobenzylamine, PABA) by grafting of a polyelectrolyte brush (poly [2-(methacryloyloxy)-ethyl-trimethylammonium chloride], PMETAC). As PABA has extra pendant amino moieties, the grafting procedure does not affect the backbone nitrogen atoms that are implicated in the electronic structure of the conducting polymers. Moreover, perchlorate anions interact very strongly with the quaternary ammonium pendant groups of PMETAC through ion pairing. Therefore, the grafting does not only keep the electroactivity of PABA in aqueous solutions but it adds the ion-actuation properties of the PMETAC brush to the modified electrode as demonstrated by contact angle measurements and electrochemical methods. In this way, the conjugation of the electron transfer properties of the conducting polymer with the anion responsiveness of the integrated brush renders perchlorate actuation of the electrochemical response. These results constitute a rational integration of nanometer-sized polymer building blocks that yields synergism of functionalities and illustrate the potentialities of nanoarchitectonics for pushing the limits of soft material science into the nanoworld. Copyright © 2018 Elsevier Inc. All rights reserved.

Assessment of polyelectrolyte coating stability under dynamic buffer conditions in CE.

PubMed

Swords, Kyleen E; Bartline, Peter B; Roguski, Katherine M; Bashaw, Sarah A; Frederick, Kimberley A

2011-09-01

Dynamic buffer conditions are present in many electrophoretically driven separations. Polyelectrolyte multilayer coatings have been employed in CE because of their chemical and physical stability as well as their ease of application. The goal of this study is to measure the effect of dynamic changes in buffer pH on flow using a real-time method for measuring EOF. Polyelectrolyte multilayers (PEMs) were composed of pairs of strong or completely ionized polyelectrolytes including poly(diallyldimethylammonium) chloride and poly(styrene sulfonate) and weak or ionizable polyelectrolytes including poly(allylamine) and poly(methacrylic acid). Polyelectrolyte multilayers of varying thicknesses (3, 4, 7, 8, 15, or 16 layers) were also studied. While the magnitude of the EOF was monitored every 2 s, the buffer pH was exchanged from a relatively basic pH (7.1) to increasingly acidic pHs (6.6, 6.1, 5.5, and 5.1). Strong polyelectrolytes responded minimally to changes in buffer pH (<1%), whereas substantial (>10%) and sometimes irreversible changes were measured with weak polyelectrolytes. Thicker coatings resulted in a similar magnitude of response but were more likely to degrade in response to buffer pH changes. The most stable coatings were formed from thinner layers of strong polyelectrolytes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Driving Forces of the Self-Assembly of Supramolecular Systems: Partially Ordered Mesophases

NASA Astrophysics Data System (ADS)

Shcherbina, M. A.; Chvalun, S. N.

2018-06-01

The main aspects are considered of the self-organization of a new class of liquid crystalline compounds, rigid sector-shaped and cone-shaped dendrons. Theoretical approaches to the self-assembly of different amphiphilic compounds (lipids, bolaamphiphiles, block copolymers, and polyelectrolytes) are described. Particular attention is given to the mesophase structures that emerge during the self-organization of mesophases characterized by intermediate degrees of ordering, e.g., plastic crystals, the rotation-crystalline phase in polymers, ordered and disordered two-dimensional columnar phases, and bicontinuous cubic phases of different symmetry.

Characterization and cell behavior of titanium surfaces with PLL/DNA modification via a layer-by-layer technique.

PubMed

Gao, Wenli; Feng, Bo; Lu, Xiong; Wang, Jianxin; Qu, Shuxin; Weng, Jie

2012-08-01

This study describes the fabrication of two types of multilayered films onto titanium by layer-by-layer (LBL) self-assembly, using poly-L-lysine (PLL) as the cationic polyelectrolyte and deoxyribonucleic acid (DNA) as the anionic polyelectrolyte. The assembling process of each component was studied using atomic force microscopy (AFM) and quartz crystal balance (QCM). Zeta potential of the LBL-coated microparticles was measured by dynamic light scattering. Titanium substrates with or without multilayered films were used in osteoblast cell culture experiments to study cell proliferation, viability, differentiation, and morphology. Results of AFM and QCM indicated the progressive build-up of the multilayered coatings. The surface morphology of three types of multilayered films showed elevations in the nanoscale range. The data of zeta potential showed that the surface terminated with PLL displayed positive charge while the surface terminated with DNA displayed negative charge. The proliferation of osteoblasts on modified titanium films was found to be greater than that on control (p < 0.05) after 3 and 7 days culture, respectively. Alamar blue measurement showed that the PLL/DNA-modified films have higher cell viability (p < 0.05) than the control. Still, the alkaline phosphatase activity assay revealed a better differentiated phenotype on three types of multilayered surfaces compared to noncoated controls. Collectively our results suggest that PLL/DNA were successfully used to surface engineer titanium via LBL technique, and enhanced its cell biocompatibility. Copyright © 2012 Wiley Periodicals, Inc.

Multilayer polyelectrolyte films functionalized by insertion of defensin: a new approach to protection of implants from bacterial colonization.

PubMed

Etienne, O; Picart, C; Taddei, C; Haikel, Y; Dimarcq, J L; Schaaf, P; Voegel, J C; Ogier, J A; Egles, C

2004-10-01

Infection of implanted materials by bacteria constitutes one of the most serious complications following prosthetic surgery. In the present study, we developed a new strategy based on the insertion of an antimicrobial peptide (defensin from Anopheles gambiae mosquitoes) into polyelectrolyte multilayer films built by the alternate deposition of polyanions and polycations. Quartz crystal microbalance and streaming potential measurements were used to follow step by step the construction of the multilayer films and embedding of the defensin within the films. Antimicrobial assays were performed with two strains: Micrococcus luteus (a gram-positive bacterium) and Escherichia coli D22 (a gram-negative bacterium). The inhibition of E. coli D22 growth at the surface of defensin-functionalized films was found to be 98% when 10 antimicrobial peptide layers were inserted in the film architecture. Noticeably, the biofunctionalization could be achieved only when positively charged poly(l-lysine) was the outermost layer of the film. On the basis of the results of bacterial adhesion experiments observed by confocal or electron microscopy, these observations could result from the close interaction of the bacteria with the positively charged ends of the films, which allows defensin to interact with the bacterial membrane structure. These results open new possibilities for the use of such easily built and functionalized architectures onto any type of implantable biomaterial. The modified surfaces are active against microbial infection and represent a novel means of local host protection.

Cucurbit[8]uril-Containing Multilayer Films for the Photocontrolled Binding and Release of a Guest Molecule.

PubMed

Nicolas, Henning; Yuan, Bin; Zhang, Xi; Schönhoff, Monika

2016-03-15

The powerful host-guest chemistry of cucurbit[8]uril (CB[8]) was employed to obtain photoresponsive polyelectrolyte multilayer films for the reversible and photocontrolled binding and release of an organic guest molecule. For this purpose, we designed and synthesized a polyelectrolyte with azobenzene side groups. Then, CB[8] was associated with the azo side group to obtain a supramolecular host-guest complex that was further used as building block in order to prepare photoresponsive and CB[8]-containing polyelectrolyte multilayer films. Ultraviolet spectroscopy and a dissipative quartz crystal microbalance are employed to monitor the formation of the host-guest complex and the layer-by-layer self-assembly of the multilayer films, respectively. We demonstrate that the photoresponsive properties of the azo side groups are maintained before and after host-guest complexation with CB[8] in solution and within the multilayer films, respectively. A guest molecule was then specifically included as second binding partner into the CB[8]-containing multilayer films. Subsequently, the release of the guest was performed by UV light irradiation due to the trans-cis isomerization of the adjacent azo side groups. Re-isomerization of the azo side groups was achieved by VIS light irradiation and enabled the rebinding of the guest into CB[8]. Finally, we demonstrate that the photocontrolled binding and release within CB[8]-containing multilayer films can reliably and reversibly be performed over a period of more than 2 weeks with constant binding efficiency. Therefore, we expect such novel type of photosensitive films to have promising future applications in the field of stimuli-responsive nanomaterials.

Polyelectrolyte brushes on dielectric surfaces

NASA Astrophysics Data System (ADS)

Antila, Hanne; Luijten, Erik

When chains of charged polymers are grafted to a solid surface, a polyelectrolyte (PE) brush results. These types of PE assemblies have a wide range of applications ranging from fuel cells and switchable electrodes to drug delivery. Many of these applications stem from the ability of PE brushes to respond to external stimuli: the brush properties can be tuned, for example, by varying electric field, PE grafting density, pH, salt concentration or salt valency. Accordingly, deciphering the brush behavior under different conditions has been a subject of considerable experimental, theoretical, and computational research efforts. However, the effect of the dielectric properties of the substrate on the PE brush has received much less attention. We use coarse-grained molecular dynamics simulations to show how varying the dielectric mismatch between the solvent and the substrate can significantly affect the brush. We demonstrate how tuning this mismatch can either diminish or enhance the effects of other control parameters, such as pH, on the brush properties. Furthermore, we investigate how dielectric properties of the substrate affect the brush, and the ion distribution and mobility within the brush, when the brush is exposed to an electric field.

Light and dark-activated biocidal activity of conjugated polyelectrolytes.

PubMed

Ji, Eunkyung; Corbitt, Thomas S; Parthasarathy, Anand; Schanze, Kirk S; Whitten, David G

2011-08-01

This Spotlight on Applications provides an overview of a research program that has focused on the development and mechanistic study of cationic conjugated polyelectrolytes (CPEs) that function as light- and dark-active biocidal agents. Investigation has centered on poly-(phenylene ethynylene) (PPE) type conjugated polymers that are functionalized with cationic quaternary ammonium solubilizing groups. These polymers are found to interact strongly with Gram-positive and Gram-negative bacteria, and upon illumination with near-UV and visible light act to rapidly kill the bacteria. Mechanistic studies suggest that the cationic PPE-type polymers efficiently sensitize singlet oxygen ((1)O(2)), and this cytotoxic agent is responsible for initiating the sequence of events that lead to light-activated bacterial killing. Specific CPEs also exhibit dark-active antimicrobial activity, and this is believed to arise due to interactions between the cationic/lipophilic polymers and the negatively charged outer membrane characteristic of Gram-negative bacteria. Specific results are shown where a cationic CPE with a degree of polymerization of 49 exhibits pronounced light-activated killing of E. coli when present in the cell suspension at a concentration of 1 μg mL(-1).

Ion transport and selectivity in biomimetic nanopores with pH-tunable zwitterionic polyelectrolyte brushes.

PubMed

Zeng, Zhenping; Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi

2015-10-28

Inspired by nature, functionalized nanopores with biomimetic structures have attracted growing interests in using them as novel platforms for applications of regulating ion and nanoparticle transport. To improve these emerging applications, we study theoretically for the first time the ion transport and selectivity in short nanopores functionalized with pH tunable, zwitterionic polyelectrolyte (PE) brushes. In addition to background salt ions, the study takes into account the presence of H(+) and OH(-) ions along with the chemistry reactions between functional groups on PE chains and protons. Due to ion concentration polarization, the charge density of PE layers is not homogeneously distributed and depends significantly on the background salt concentration, pH, grafting density of PE chains, and applied voltage bias, thereby resulting in many interesting and unexpected ion transport phenomena in the nanopore. For example, the ion selectivity of the biomimetic nanopore can be regulated from anion-selective (cation-selective) to cation-selective (anion-selective) by diminishing (raising) the solution pH when a sufficiently small grafting density of PE chains, large voltage bias, and low background salt concentration are applied.

Multiscale treatment of theoretical mechanisms for the protection of hydrogel surfaces from adhesive forces

NASA Astrophysics Data System (ADS)

Sokoloff, J. B.

2014-09-01

One role of a lubricant is to prevent wear of two surfaces in contact, which is likely to be the result of adhesive forces that cause a pair of asperities belonging to two surfaces in contact to stick together. Such adhesive sticking of asperities can occur both for sliding surfaces and for surfaces which are pressed together and then pulled apart. The latter situation, for example, is important for contact lenses, as prevention of sticking reduces possible damage to the cornea as the lenses are inserted and removed from the eye. Contact lenses are made from both neutral and polyelectrolyte hydrogels. It is demonstrated here that sticking of neutral hydrogels can be prevented by repulsive forces between asperities in contact, resulting from polymers attached to the gel surface but not linked with each other. For polyelectrolyte hydrogels, it is shown that osmotic pressure due to counterions, held at the interface between asperities in contact by the electrostatic attraction between the ions and the fixed charges in the gel, can provide a sufficiently strong repulsive force to prevent adhesive sticking of small-length-scale asperities.

Macroion induced dehydration of weak polyelectrolyte brushes

NASA Astrophysics Data System (ADS)

Zheng, Zhongli; Zhu, Y. Elaine

2014-03-01

The interaction of macroions, including polyelectrolytes, DNAs, and proteins, with polymer and cellular surfaces is critically related to many biomolecular activities, such as protein adsorption and DNA hybridization at probe surfaces. In an experimental approach to examine the macroion electrostatic interaction with a polymer surface while minimizing the long-debated hydrophobic interaction, we study the interaction of molybdenum-based inorganic polyoxometalate (POM) nanoclusters carrying 42 negative charges as model hydrophilic macroions with surface-tethered poly-2-vinylpyridine (P2VP) brushes immersed in aqueous solutions. By AFM, QCM, and contact goniometer, we have observed the collapse of P2VP chains by adding POM macroions at a constant pH. Surprisingly, added POM macroions can cause the shift of swollen-to-collapse transition pH to a lower value, in contrast to the shift to high pH value by adding simple monovalent salts. At sufficiently high POM concentration, a stable POM-P2VP composite layer, showing little dependence on solution pH and additional salts, can be formed, suggesting a simple route to construct meso-porous polymer membranes.

Osmotic Pressure in Ionic Microgel Dispersions

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2015-03-01

Microgels are microscopic gel particles, typically 10-1000 nm in size, that are swollen by a solvent. Hollow microgels (microcapsules) can encapsulate cargo, such as dye molecules or drugs, in their solvent-filled cavities. Their sensitive response to environmental conditions (e.g., temperature, pH) and influence on flow properties suit microgels to widespread applications in the chemical, pharmaceutical, food, and consumer care industries. When dispersed in water, polyelectrolyte gels become charged through dissociation of counterions. The electrostatic contribution to the osmotic pressure inside and outside of ionic microgels influences particle swelling and bulk materials properties, including thermodynamic, structural, optical, and rheological properties. Within the primitive and cell models of polyelectrolyte solutions, we derive an exact statistical mechanical formula for the contribution of mobile microions to the osmotic pressure within ionic microgels. Using Poisson-Boltzmann theory, we validate this result by explicitly calculating ion distributions across the surface of an ionic microgel and the electrostatic contribution to the osmotic pressure. Within a coarse-grained one-component model, we further chart the limits of the cell model for salty dispersions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

Tuning the properties of conjugated polyelectrolytes and application in a biosensor platform

DOEpatents

Chen, Liaohai

2004-05-18

The present invention provides a method of detecting a biological agent including contacting a sample with a sensor including a polymer system capable of having an alterable measurable property from the group of luminescence, anisotropy, redox potential and uv/vis absorption, the polymer system including an ionic conjugated polymer and an electronically inert polyelectrolyte having a biological agent recognition element bound thereto, the electronically inert polyelectrolyte adapted for undergoing a conformational structural change upon exposure to a biological agent having affinity for binding to the recognition element bound to the electronically inert polyelectrolyte, and, detecting the detectable change in the alterable measurable property. A chemical moiety being the reaction product of (i) a polyelectrolyte monomer and (ii) a biological agent recognition element-substituted polyelectrolyte monomer is also provided.

Spectrally resolved single-molecule electrometry

NASA Astrophysics Data System (ADS)

Ruggeri, F.; Krishnan, M.

2018-03-01

Escape-time electrometry is a recently developed experimental technique that offers the ability to measure the effective electrical charge of a single biomolecule in solution with sub-elementary charge precision. The approach relies on measuring the average escape-time of a single charged macromolecule or molecular species transiently confined in an electrostatic fluidic trap. Comparing the experiments with the predictions of a mean-field model of molecular electrostatics, we have found that the measured effective charge even reports on molecular conformation, e.g., folded or disordered state, and non-uniform charge distribution in disordered proteins or polyelectrolytes. Here we demonstrate the ability to use the spectral dimension to distinguish minute differences in electrical charge between individual molecules or molecular species in a single simultaneous measurement, under identical experimental conditions. Using one spectral channel for referenced measurement, this kind of photophysical distinguishability essentially eliminates the need for accurate knowledge of key experimental parameters, otherwise obtained through intensive characterization of the experimental setup. As examples, we demonstrate the ability to detect small differences (˜5%) in the length of double-stranded DNA fragments as well as single amino acid exchange in an intrinsically disordered protein, prothymosin α.

Phase behavior and structure of stable complexes between a long polyanion and a branched polycation

NASA Astrophysics Data System (ADS)

Mengarelli, Valentina; Zeghal, Mehdi; Auvray, Loïc; Clemens, Daniel

2011-08-01

The association between oppositely charged branched polyethylenimine (BPEI) and polymethacrylic acid (PMA) in the dilute regime is investigated using turbidimetric titration and electrophoretic mobility measurements. The complexation is controlled by tuning continuously the pH-sensitive charge of the polyacid in acidic solution. The formation of soluble and stable positively charged complexes is a cooperative process characterized by the existence of two regimes of weak and strong complexation. In the regime of weak complexation, a long PMA chain overcharged by several BPEI molecules forms a binary complex. As the charge of the polyacid increases, these binary complexes condense at a well defined charge ratio of the mixture to form large positively charged aggregates. The overcharging and the existence of two regimes of complexation are analyzed in the light of recent theories. The structure of the polyelectrolytes is investigated at higher polymer concentration by small angle neutron scattering. Binary complexes of finite size present an open structure where the polyacid chains connecting a small number of BPEI molecules have shrunk slightly. In the condensed complexes, BPEI molecules, wrapped by polyacid chains, form networks of stretched necklaces.

Thermodynamic and kinetic control of charged, amphiphilic triblock copolymer assembly via interaction with organic counterions in solvent mixtures

NASA Astrophysics Data System (ADS)

Cui, Honggang

2007-12-01

Amphiphilic block copolymers, consisting of at least two types of monomers with different affinity to the dissolving solvent(s), have been recognized as a molecular building unit for their chemical tunability and design flexibility. Amphiphilic block copolymers with a chargeable block have structural features of polyelectrolytes, block copolymers and surfactants. The combination of these different features offers great flexibility for developing novel assembled morphologies at the nanoscale and outstanding ability to control and manipulate those morphologies. The nanostructures, formed from the spontaneous association of amphiphilic block copolymer in selective solvents, show promise for applications in nanotechnology and pharmaceuticals, including drug delivery, tissue engineering and bio-imaging. A basic knowledge of their modes of self-assembly and their correspondence to application-related properties is just now being developed and poses a considerable scientific challenge. The goal of this dissertation is to investigate the associative behavior of charged, amphiphilic block copolymers in solvent mixtures while in the presence of organic counterions. Self-assembly of poly (acrylic acid)- block-poly (methyl acrylate)-block-polystyrene (PAA- b-PMA-b-PS) triblock copolymers produces nanodomains in THF/water solution specifically through the interaction with organic counterions (polyamines). These assembled structures can include classic micelles (spheres, cylinders and vesicles), but, more importantly, include non-classic micelles (disks, toroids, branched micelles and segmented micelles). Each micelle structure is stable and reproducible at different assembly conditions. The assembled micellar structures depend on not only solution components (thermodynamics) but also mixing procedure and consequent self-assembly pathway (kinetics). The key factors that determine the thermodynamic interactions that partially define the assembled structures and the kinetic assembly process include THF/water ratio, PS block length, the type and amount of organic counterions, and the mixing pathway. Their formation mechanism has been investigated from three aspects: (i) the chain structure of organic counterions, including spacer length, chain hydrophobicity between ionizable groups and the number of ionizable groups (amine group); (ii) molecular structure of the triblock copolymer, including block length of polystyrene and chain architecture; (iii) relative variation of the components, such as different ratios of THF to water and the different ratios of amine groups to acid groups. The first example of a novel micelle formed was the toroidal micelle. The toroidal micelle morphology, which is theoretically predicted but rarely observed, has been produced by the self assembly of PAA99- b-PMA73-b-PS66 in combination with 2,2-(ethylenedioxy)diethylamine (EDDA) and mixed THF/H2O solvent. It was found that toroids can be constructed by two mechanisms: elimination of energetically unfavored cylindrical micelle endcaps or perforation of disk-like micelles. Three-fold junctions were formed as intermediate structures to facilitate toroidal formation from cylindrical micelles. In order to construct toroids from cylindrical micelles, three requirements must be met: lower bending modulus (flexibility of cylinders), selfattraction between cylinders, and extra endcapping energy originating from chain packing frustration. Extremely high energy spheres can also fuse into toroids. Disk-like micelles can transform into a toroidal morphology when cylindrical packing geometry was initiated along the rims of disk-like micelles via solvent mixing that eventually perforated the disk center. The toroidal morphology can be kinetically trapped by either ridding the system of organic solvent or chemically crosslinking the PAA corona with EDDA via addition of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (DPEM). The interaction of positively-charged, multivalent organic amines with the negatively-charged PAA corona plays a decisive role in the formation of these micelles. Inter-chain binding from the interaction of the two amine end groups of diamines with acid groups from different PAA corona blocks governs the final assembled structures. Diamines with hydrophilic spacers induced the formation of micelles with larger interfacial curvature as the spacer length increased. Disk-like micelles, cylindrical micelles or spherical micelles were observed with the gradual increase of hydrophilic spacer length. Diamines with variable hydrophobic spacers showed a similar effect when the spacer length was less than six methylene units. Application of longer hydrophobic diamines had a reverse effect on the interfacial curvature. This effect was attributed to the interaction of hydrophobic diamine hydrocarbon linking chains with the PMA-b-PS hydrophobic core. These findings indicate an easy method to tune micelle structure with multivalent organic counterions. (Abstract shortened by UMI.)

Multicompartmental Microcapsules from Star Copolymer Micelles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Ikjun; Malak, Sidney T.; Xu, Weinan

2013-02-26

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into themore » LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.« less

From the 2-dimensional unstable polyelectrolyte multilayer to the 3-dimensional stable dry polyelectrolyte capsules.

PubMed

Li, Xiaodong; Zhang, Jianxiang; Hu, Qiaoling; Li, Xiaohui

2011-11-01

Polystyrene-poly(acrylic acid)/poly(allylamine hydrochloride) polyelectrolyte multilayer was found to be instable and apt to reconstruct in the pure water. By depositing polystyrene-poly(acrylic acid)/poly(allylamine hydrochloride) multilayer on the polystyrene-poly(acrylic acid) hybrid CaCO(3) templates, novel polyelectrolyte capsules could be prepared after the removal of the templates. The resultant capsules could keep their three-dimensional (3D) spherical shape after being dried at room temperature, dramatically different from the conventional polyelectrolyte capsules based on nonhybrid templates by layer-by-layer procedure. The instable polyelectrolyte multilayer, hybrid templates, and assembly cycles were demonstrated to be three indispensable factors responsible for the formation of this type of 3D stable capsules. The formation mechanism was also discussed in this study. Copyright © 2011 Elsevier Inc. All rights reserved.

Polycation-sodium lauryl ether sulfate-type surfactant complexes: influence of ethylene oxide length.

PubMed

Vleugels, Leo F W; Pollet, Jennifer; Tuinier, Remco

2015-05-21

Polyelectrolyte-surfactant complexes (PESC) are a class of materials which form spontaneously by self-assembly driven by electrostatic and hydrophobic interactions. PESC containing sodium lauryl ether sulfates (SLES) have found wide application in hair care products like shampoo. Typically, SLES with only one or two ethylene oxide (EO) groups are used for this application. We have studied the influence of the size of the EO block (ranging from 0 to 30 EO groups) on complexation with two model polycations: linear polyDADMAC and branched PEI. PESC size and electrostatic properties were determined during stepwise titration of buffered polycation solutions. The critical aggregation concentration (CAC) of PESC was determined by surface tension measurements and fluorescence spectroscopy. For polyDADMAC, there is no influence of the size of the EO block on the complexation behavior; the stiff polycation governs the structure formation. For PEI, it was seen that the EO block size does affect the structure of the complexes. The CAC value of the investigated complexes turns out to be rather independent of the EO block size; however, the CMC/CAC ratio decreases with increasing size of the EO block. This latter observation explains why the Lochhead-Goddard effect is most effective for small EO blocks.

Proton and metal ion binding to natural organic polyelectrolytes-I. Studies with synthetic model compounds

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1984-01-01

A unified physico-chemical model, based on a modified Henderson-Hasselbalch equation, for the analysis of ion complexation reactions involving charged polymeric systems is presented and verified. In this model pH = pKa+p(??Ka) + log(??/1 - ??) where Ka is the intrinsic acid dissociation constant of the ionizable functional groups on the polymer, ??Ka is the deviation of the intrinsic constant due to electrostatic interaction between the hydrogen ion and the polyanion, and alpha (??) is the polyacid degree of ionization. Using this approach pKa values for repeating acidic units of polyacrylic (PAA) and polymethacrylic (PMA) acids were found to be 4.25 ?? 0.03 and 4.8 ?? 0.1, respectively. The polyion electrostatic deviation term derived from the potentiometric titration data (i.e. p(??Ka)) is used to calculate metal ion concentration at the complexation site on the surface of the polyanion. Intrinsic cobalt-polycarboxylate binding constants (7.5 for PAA and 5.6 for PMA), obtained using this procedure, are consistent with the range of published binding constants for cobalt-monomer carboxylate complexes. In two phase systems incorporation of a Donnan membrane potential term allows determination of the intrinsic pKa of a cross-linked PMA gel, pKa = 4.83, in excellent agreement with the value obtained for the linear polyelectrolyte and the monomer. Similarly, the intrinsic stability constant for cobalt ion binding to a PMA-gel (??CoPMA+ = 11) was found to be in agreement with the linear polyelectrolyte analogue and the published data for cobalt-carboxylate monodentate complexes. ?? 1984.

pH-responsive ion transport in polyelectrolyte multilayers of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA) bearing strong- and weak anionic groups.

PubMed

Maza, Eliana; Tuninetti, Jimena S; Politakos, Nikolaos; Knoll, Wolfgang; Moya, Sergio; Azzaroni, Omar

2015-11-28

The layer-by-layer construction of interfacial architectures displaying stimuli-responsive control of mass transport is attracting increasing interest in materials science. In this work, we describe the creation of interfacial architectures displaying pH-dependent ionic transport properties which until now have not been observed in polyelectrolyte multilayers. We describe a novel approach to create pH-controlled ion-rectifying systems employing polyelectrolyte multilayers assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA), alternately deposited with poly(diallyldimethylammonium chloride) (PDADMAC). The conceptual framework is based on the very contrasting and differential interactions of PSS and MA units with PDADMAC. In our setting, sulfonate groups play a structural role by conferring stability to the multilayer due to the strong electrostatic interactions with the polycations, while the weakly interacting MA groups remain "silent" within the film and then act as on-demand pH-responsive units. When these multilayers are combined with a strong cationic capping layer that repels the passage of cationic probes, a pH-gateable rectified transport of anions is observed. Concomitantly, we also observed that these functional properties are significantly affected when multilayers are subjected to extensive pH cycling as a consequence of irreversible morphological changes taking place in the film. We envision that the synergy derived from combining weak and strong interactions within the same multilayer will play a key role in the construction of new interfacial architectures displaying tailorable ion transport properties.

Volumetric and calorimetric properties of aqueous ionene solutions

PubMed Central

Lukšič, Miha; Hribar-Lee, Barbara

2016-01-01

The volumetric (partial and apparent molar volumes) and calorimetric properties (apparent heat capacities) of aqueous cationic polyelectrolyte solutions – ionenes – were studied using the oscillating tube densitometer and differential scanning calorimeter. The polyion’s charge density and the counterion properties were considered as variables. The special attention was put to evaluate the contribution of electrostatic and hydrophobic effects to the properties studied. The contribution of the CH2 group of the polyion’s backbone to molar volumes and heat capacities was estimated. Synergistic effect between polyion and counterions was found. PMID:28503012

Artificial phosphorylation sites modulate the activity of a voltage-gated potassium channel

NASA Astrophysics Data System (ADS)

Ariyaratne, Amila; Zocchi, Giovanni

2015-03-01

The KvAP potassium channel is representative of a family of voltage-gated ion channels where the membrane potential is sensed by a transmembrane helix containing several positively charged arginines. Previous work by Wang and Zocchi [A. Wang and G. Zocchi, PLoS ONE 6, e18598 (2011), 10.1371/journal.pone.0018598] showed how a negatively charged polyelectrolyte attached in proximity to the voltage sensing element can bias the opening probability of the channel. Here we introduce three phosphorylation sites at the same location and show that the response curve of the channel shifts by about 20 mV upon phosphorylation, while other characteristics such as the single-channel conductance are unaffected. In summary, we construct an artificial phosphorylation site which confers allosteric regulation to the channel.

Preparation of ionic membranes for zinc/bromine storage batteries

NASA Astrophysics Data System (ADS)

Assink, R. A.; Arnold, C., Jr.

Zinc/bromine flow batteries are being developed for vehicular and utility load leveling applications. During charge, an aqueous zinc bromide salt is electrolyzed to zinc metal and molecular bromine. During discharge, the zinc and bromine react to again form the zinc bromide salt. One serious disadvantage of the microporous separators presently used in the zinc/bromine battery is that modest amounts of bromine and negatively charged bromine moieties permeate through these materials and react with the zinc anode. This results in partial self-discharge of the battery and low coulombic efficiencies. Our approach to this problem is to impregnate the microporous separators with a soluble cationic polyelectrolyte. In laboratory screening tests a sulfonated polysulfone resin and fully fluorinated sulfonic acid polymer substantially reduced bromine permeation with only modest increases in the area resistance.

Aquifer modification: an approach to improve the mobility of nanoscale zero-valent iron particles used for in situ groundwater remediation

NASA Astrophysics Data System (ADS)

MicicBatka, Vesna; Schmid, Doris; Marko, Florian; Velimirovic, Milica; Wagner, Stephan; von der Kammer, Frank; Hofmann, Thilo

2015-04-01

Successful emplacement of nanoscale zero-valent iron (nZVI) within the contaminated source zone is a prerequisite for the use of nZVI technology in groundwater remediation. Emplacement of nZVI is influenced i.e., by the injection technique and the injection velocity applied, as well as by the mobility of nZVI in the subsurface. Whereas processes linked to the injection can be controlled by the remediation practitioners, the mobility of nZVI in the subsurface remains limited. Even though mobility of nZVI is somewhat improved by surface coating with polyelectrolytes, it is still greatly affected by the groundwater composition and physical and chemical heterogeneities of aquifer grains. In order to promote mobility of nZVI it is needed to alter the surface charge heterogeneities of aquifer grains. Modifying the aquifer grain's surfaces by means of polyelectrolyte coating is an approach proposed to increase the overall negative surface charge of the aquifer grain surfaces, hinder deposition of nZVI onto aquifer grains, and finally promote nZVI mobility. In this study the effect of different polyelectrolytes on the nZVI mobility is tested in natural sands deriving from real brownfield sites that are proposed to be remediated using the nZVI technology. Sands collected from brownfield sites were characterized in terms of grain size distribution, mineralogical and chemical composition, and organic carbon content. Furthermore, surface charge of these sands was determined in both, low- and high ionic strength background solutions. Finally, changes of the sand's surface charges were examined after addition of the proposed aquifer modifiers, lignin sulfonate and humic acid. Surface charge of brownfield sands in low ionic strength background solution is more negative compared to that in high ionic strength background solution. An increase in negative surface potential of brownfield sand was recorded when aquifer modifiers were applied in a background solution with low ionic strength, indicating their potential to improve nZVI mobility under comparable environmental conditions. In contrast, no significant change of the surface potential of brownfield sand was observed when aquifer modifiers were applied in a background solution with high ionic strength. The potential of the aquifer modifiers to promote the mobility of nZVI was furthermore tested in flow-through columns, starting with the one filled with natural quartz sand with rough surface, low ionic strength background solutions and pre-injecting lignin sulfonate in concentration of 50 mg/L. The preliminary results showed that the pre-injection of lignin sulfonate does increase mobility of nZVI under this experimental condition. Further mobility tests will be carried out in order to elucidate the potential of the aquifer modifiers to promote the mobility of nZVI in sands with a complex mineralogy and in the background solutions with varying ionic strength, in order to account for the condition that resemble those at polluted sites. This research receives funding from the European Union's Seventh Framework Programme FP7/2007-2013 under grant agreement n°309517.

[Inclusion of proteins into polyelectrolyte microcapsules by coprecipitation and adsorption].

PubMed

Kochetkova, O Iu; Kazakova, L I; Moshkov, D A; Vinokurov, M G; Shabarchina, L I

2013-01-01

In present study microcapsules composed of synthetic (PSS and PAA) and biodegradable (DS and PAr) polyelectrolytes on calcium carbonate microparticles were obtained. The ultrastructural organization of biodegradable microcapsules was studied using transmission electron microscopy. The envelope of such capsules consisting of six polyelectrolyte layers is already well-formed, having the average thickness of 44 ± 3.0 nm, and their internal polyelectrolyte matrix is sparser compared to the synthetic microcapsules. Spectroscopy was employed to evaluate the efficiency of incorporation of FITC-labeled BSA into synthetic microcapsules by adsorption, depending on the number of polyelectrolyte layers. It was shown that the maximal amount of protein incorporated into the capsules with 6 or 7 polyelectrolyte layers (4 and 2 pg/capsule, correspondingly). As a result we conclude that, in comparison with co-precipitation, the use of adsorption allows to completely avoid the loss of protein upon encapsulation.

LASERS, ACTIVE MEDIA: The aqueous-polyelectrolyte dye solution as an active laser medium

NASA Astrophysics Data System (ADS)

Akimov, A. I.; Saletskii, A. M.

2000-11-01

The spectral, luminescent, and lasing properties of aqueous solutions of a cationic dye rhodamine 6G with additions of anion polyelectrolytes — polyacrylic and polymethacrylic acids — are studied. It is found that the energy and spectral properties of lasing of these solutions depend on the ratio of concentrations of polyelectrolyte and molecules. It is also found that the lasing parameters of aqueous-polyelectrolyte dye solutions can be controlled by changing the structure of the molecular system. The variation in the structure of aqueous-polyelectrolyte dye solutions of rhodamine 6G resulted in an almost five-fold increase in the lasing efficiency compared to that in aqueous dye solutions.

Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1991-01-01

Earlier research has shown that the acid dissociation and metal ion complexation equilibria of linear, weak-acid polyelectrolytes and their cross-linked gel analogues are similarly sensitive to the counterion concentration levels of their solutions. Gibbs-Donnan-based concepts, applicable to the gel, are equally applicable to the linear polyelectrolyte for the accommodation of this sensitivity to ionic strength. This result is presumed to indicate that the linear polyelectrolyte in solution develops counterion-concentrating regions that closely resemble the gel phase of their analogues. Advantage has been taken of this description of linear polyelectrolytes to estimate the solvent uptake by these regions. ?? 1991 American Chemical Society.

Gramicidin ion channels in a lipid bilayer supported on polyelectrolyte multilayer films: an electrochemical impedance study.

PubMed

Diamanti, Eleftheria; Gutiérrez-Pineda, Eduart; Politakos, Nikolaos; Andreozzi, Patrizia; Rodriguez-Presa, María José; Knoll, Wolfgang; Azzaroni, Omar; Gervasi, Claudio A; Moya, Sergio E

2017-12-06

Supported membranes on polymer cushions are of fundamental interest as models for cell membranes. The use of polyelectrolyte multilayers (PEMs) assembled by the layer by layer (LbL) technique as supports for a bilayer allows for easy integration of the lipid bilayer on surfaces and devices and for nanoscale tunable spacing of the lipid bilayer. Controlling ionic permeability in lipid bilayers supported on PEMs triggers potential applications in sensing and as models for transport phenomena in cell membranes. Lipid bilayers displaying gramicidin channels are fabricated on top of polyallylamine hydrochloride (PAH) and polystyrene sulfonate (PSS) multilayer films, by the assembly of vesicles of phosphatidylcholine and phosphatidylserine, 50 : 50 M/M, carrying gramicidin (GA). Quartz crystal microbalance with dissipation shows that the vesicles with GA fuse into a bilayer. Atomic force microscopy reveals that the presence of GA alters the bilayer topography resulting in depressions in the bilayer of around 70 nm in diameter. Electrochemical impedance spectroscopy (EIS) studies show that supported bilayers carrying GA have smaller resistances than the bilayers without GA. Lipid layers carrying GA display a higher conductance for K + than for Na + and are blocked in the presence of Ca 2+ .

High-performance serial block-face SEM of nonconductive biological samples enabled by focal gas injection-based charge compensation.

PubMed

Deerinck, T J; Shone, T M; Bushong, E A; Ramachandra, R; Peltier, S T; Ellisman, M H

2018-05-01

A longstanding limitation of imaging with serial block-face scanning electron microscopy is specimen surface charging. This charging is largely due to the difficulties in making biological specimens and the resins in which they are embedded sufficiently conductive. Local accumulation of charge on the specimen surface can result in poor image quality and distortions. Even minor charging can lead to misalignments between sequential images of the block-face due to image jitter. Typically, variable-pressure SEM is used to reduce specimen charging, but this results in a significant reduction to spatial resolution, signal-to-noise ratio and overall image quality. Here we show the development and application of a simple system that effectively mitigates specimen charging by using focal gas injection of nitrogen over the sample block-face during imaging. A standard gas injection valve is paired with a precisely positioned but retractable application nozzle, which is mechanically coupled to the reciprocating action of the serial block-face ultramicrotome. This system enables the application of nitrogen gas precisely over the block-face during imaging while allowing the specimen chamber to be maintained under high vacuum to maximise achievable SEM image resolution. The action of the ultramicrotome drives the nozzle retraction, automatically moving it away from the specimen area during the cutting cycle of the knife. The device described was added to a Gatan 3View system with minimal modifications, allowing high-resolution block-face imaging of even the most charge prone of epoxy-embedded biological samples. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Impact of organic polyelectrolytes on coagulation of source-separated black water.

PubMed

Kozminykh, Pavlo; Heistad, Arve; Ratnaweera, Harsha C; Todt, Daniel

2016-01-01

Household wastewater is originated from common people's activities and has a potential harmful impact on the environment if discharged directly without proper treatment. Toilet wastewater or black water (BW) contains urine, faeces, toilet paper and flushing water and it contains the majority of pollutants obtained from a single household. In this study, the focus was on BW treatment using chemical methods. The main goal of current research was to define the possibility and applicability of conventional coagulants and flocculants in direct chemical treatment of vacuum-collected BW to remove particles, organic matter and phosphorous. After the definition of dosing ranges, based on the equivalent doses in conventional municipal and industrial wastewater treatment data, aluminium and iron coagulants, organic polyelectrolytes (polymers with anionic, neutral and cationic charge with different molecular weights) and their various combinations were tested using the well-known jar-test laboratory method to study aggregation and solid-liquid separation processes in raw BW. The most important process parameter during the coagulation was pH level, dependent on the type and doses of metal salts. Some side processes were found to occur while using iron-based coagulants. Dosing of either single coagulants or single polymers did not give satisfactory results, while a combination of aluminium salts and cationic polymers showed high removal rates in total suspended solids, total chemical oxygen demand and ortho-phosphates, reaching 97.8%, 92% and 98.6%, respectively, with the optimal doses of chemicals. Cationic polymers with the lowest molecular weight and highest charge density were the most efficient in combination with aluminium coagulants.

All-nanoparticle self-assembly ZnO/TiO₂ heterojunction thin films with remarkably enhanced photoelectrochemical activity.

PubMed

Yuan, Sujun; Mu, Jiuke; Mao, Ruiyi; Li, Yaogang; Zhang, Qinghong; Wang, Hongzhi

2014-04-23

The multilaminated ZnO/TiO2 heterojunction films were successfully deposited on conductive substrates including fluorine-doped tin oxide (FTO) glass and flexible indium tin oxide coated poly(ethylene terephthalate) via the layer-by-layer (LBL) self assembly method from the oxide colloids without using any polyelectrolytes. The positively charged ZnO nanoparticles and the negatively charged TiO2 nanoparticles were directly used as the components in the consecutive deposition process to prepare the heterojunction thin films by varying the thicknesses. Moreover, the crystal growth of both oxides could be efficiently inhibited by the good connection between ZnO and TiO2 nanoparticles even after calcination at 500 °C, especially for ZnO which was able to keep the crystallite size under 25 nm. The as-prepared films were used as the working electrodes in the three-electrode photoelectrochemical cells. Because the well-contacted nanoscale heterojunctions were formed during the LBL self-assembling process, the ZnO/TiO2 all-nanoparticle films deposited on both substrates showed remarkably enhanced photoelectrochemical properties compared to that of the well-established TiO2 LBL thin films with similar thicknesses. The photocurrent response collected from the ZnO/TiO2 electrode on the FTO glass substrate was about five times higher than that collected from the TiO2 electrode. Owing to the absence of the insulating layer of dried polyelectrolytes, the ZnO/TiO2 all-nanoparticle heterojunction films were expected to be used in the photoelectrochemical device before calcination.

Mass transport in polyelectrolyte solutions

NASA Astrophysics Data System (ADS)

Schipper, F. J. M.; Leyte, J. C.

1999-02-01

The self-diffusion coefficients of the three components of a salt-free heavy-water solution of polymethacrylic acid, completely neutralized with tetra-methylammonium hydroxide, were measured over a broad concentration range. Three concentration regions were observed for the self-diffusion of both the polyions and the counterions. At polyion concentrations below 0.01 mol monomer kg-1, the dilute concentration regime for the polymer, the polyion self-diffusion coefficient approaches the self-diffusion coefficient of a freely diffusing rod upon dilution. At polyelectrolyte concentrations above 0.1 mol monomer kg-1, the self-diffusion coefficients of the solvent, the counterions and the polymer decreased with concentration, suggesting that this decrease is due to a topological constraint on the motions of the components. In the intermediate-concentration region, the self-diffusion coefficients of the polyions and the counterions are independent of the concentration. The polyion dynamic behaviour is, in the intermediate- and high-concentration regions, reasonably well described by that of a hard sphere, with a radius of 3.7 nm. A correct prediction for the solvent dynamics is given by the obstruction effect of this hard sphere on the solvent. The relative counterion self-diffusion coefficient is predicted almost quantitatively over the entire concentration range with the Poisson-Boltzmann-Smoluchowski model for the spherical cell, provided that the sphere radius and the number of charges are chosen appropriately (approximately the number of charges in a persistence length). Using this model, the dependence of the counterion self-diffusion coefficient on the ionic strength, polyion concentration and counterion radius is calculated quantitatively over a large concentration range.

Chain Conformation and Dynamics in Spin-Assisted Weak Polyelectrolyte Multilayers

DOE PAGES

Zhuk, Aliaksandr; Selin, Victor; Zhuk, Iryna; ...

2015-03-13

In this paper, we report on the effect of the deposition technique on film layering, stability, and chain mobility in weak polyelectrolyte layer-by-layer (LbL) films. Ellipsometry and neutron reflectometry (NR) showed that shear forces arising during spin-assisted assembly lead to smaller amounts of adsorbed polyelectrolytes within LbL films, result in a higher degree of internal film order, and dramatically improve stability of assemblies in salt solutions as compared to dip-assisted LbL assemblies. The underlying flattening of polyelectrolyte chains in spin-assisted LbL films was also revealed as an increase in ionization degree of the assembled weak polyelectrolytes. As demonstrated by fluorescencemore » recovery after photobleaching (FRAP), strong binding between spin-deposited polyelectrolytes results in a significant slowdown of chain diffusion in salt solutions as compared to dip-deposited films. Moreover, salt-induced chain intermixing in the direction perpendicular to the substrate is largely inhibited in spin-deposited films, resulting in only subdiffusional (<2 Å) chain displacements even after 200 h exposure to 1 M NaCl solutions. Finally, this persistence of polyelectrolyte layering has important ramifications for multistage drug delivery and optical applications of LbL assemblies.« less

Polyelectrolyte Complexes of Low Molecular Weight PEI and Citric Acid as Efficient and Nontoxic Vectors for in Vitro and in Vivo Gene Delivery.

PubMed

Giron-Gonzalez, M Dolores; Salto-Gonzalez, Rafael; Lopez-Jaramillo, F Javier; Salinas-Castillo, Alfonso; Jodar-Reyes, Ana Belen; Ortega-Muñoz, Mariano; Hernandez-Mateo, Fernando; Santoyo-Gonzalez, Francisco

2016-03-16

Gene transfection mediated by the cationic polymer polyethylenimine (PEI) is considered a standard methodology. However, while highly branched PEIs form smaller polyplexes with DNA that exhibit high transfection efficiencies, they have significant cell toxicity. Conversely, low molecular weight PEIs (LMW-PEIs) with favorable cytotoxicity profiles display minimum transfection activities as a result of inadequate DNA complexation and protection. To solve this paradox, a novel polyelectrolyte complex was prepared by the ionic cross-linking of branched 1.8 kDa PEI with citric acid (CA). This system synergistically exploits the good cytotoxicity profile exhibited by LMW-PEI with the high transfection efficiencies shown by highly branched and high molecular weight PEIs. The polyectrolyte complex (1.8 kDa-PEI@CA) was obtained by a simple synthetic protocol based on the microwave irradiation of a solution of 1.8 kDa PEI and CA. Upon complexation with DNA, intrinsic properties of the resulting particles (size and surface charge) were measured and their ability to form stable polyplexes was determined. Compared with unmodified PEIs the new complexes behave as efficient gene vectors and showed enhanced DNA binding capability associated with facilitated intracellular DNA release and enhanced DNA protection from endonuclease degradation. In addition, while transfection values for LMW-PEIs are almost null, transfection efficiencies of the new reagent range from 2.5- to 3.8-fold to those of Lipofectamine 2000 and 25 kDa PEI in several cell lines in culture such as CHO-k1, FTO2B hepatomas, L6 myoblasts, or NRK cells, simultaneously showing a negligible toxicity. Furthermore, the 1.8 kDa-PEI@CA polyelectrolyte complexes retained the capability to transfect eukaryotic cells in the presence of serum and exhibited the capability to promote in vivo transfection in mouse (as an animal model) with an enhanced efficiency compared to 25 kDa PEI. Results support the polyelectrolyte complex of LMW-PEI and CA as promising generic nonviral gene carriers.

Polyelectrolyte-modified cowpea mosaic virus for the synthesis of gold nanoparticles.

PubMed

Aljabali, Alaa A A; Evans, David J

2014-01-01

Polyelectrolyte surface-modified cowpea mosaic virus (CPMV) can be used for the templated synthesis of narrowly dispersed gold nanoparticles. Cationic polyelectrolyte, poly(allylamine) hydrochloride, is electrostatically bound to the external surface of the virus capsid. The polyelectrolyte-coated CPMV promotes adsorption of aqueous gold hydroxide anionic species, prepared from gold(III) chloride and potassium carbonate, that are easily reduced to form CPMV-templated gold nanoparticles. The process is simple and environmentally benign using only water as solvent at ambient temperature.

Adhesion of Mycobacterium smegmatis to Charged Surfaces and Diagnostics Implications

NASA Astrophysics Data System (ADS)

Gorse, Diane; Dhinojwala, Ali; Moore, Francisco

Pulmonary tuberculosis (PTB) causes more than 1 million deaths annually. Smear microscopy is a primary rapid detection tool in areas where 95 % of PTB cases occur. This technique, in which the sputum of a symptomatic patient is stained and examined using a light microscope for Mycobacterium tuberculosis (MTB) shows sensitivity between 20 and 60 %. Insufficient bacterial isolation during sample preparation may be a reason for low sensitivity. We are optimizing a system to capture bacteria on the basis of electrostatic interactions to more thoroughly isolate bacteria from suspension and facilitate more accurate detection. Silica supports coated with positively-charged polyelectrolyte, poly(diallyldimethylammonium chloride), captured approximately 4.1 times more Mycobacterium smegmatis, a model organism for MTB, than was captured on negatively-charged silica substrates. Future experimentation will employ branched polymer systems and seek to justify the use of colloidal stability theories to describe initial capture. Supported by University of Akron, Department of Polymer Science, Department of Biology; LORD Corporation.

Fast Proton Titration Scheme for Multiscale Modeling of Protein Solutions.

PubMed

Teixeira, Andre Azevedo Reis; Lund, Mikael; da Silva, Fernando Luís Barroso

2010-10-12

Proton exchange between titratable amino acid residues and the surrounding solution gives rise to exciting electric processes in proteins. We present a proton titration scheme for studying acid-base equilibria in Metropolis Monte Carlo simulations where salt is treated at the Debye-Hückel level. The method, rooted in the Kirkwood model of impenetrable spheres, is applied on the three milk proteins α-lactalbumin, β-lactoglobulin, and lactoferrin, for which we investigate the net-charge, molecular dipole moment, and charge capacitance. Over a wide range of pH and salt conditions, excellent agreement is found with more elaborate simulations where salt is explicitly included. The implicit salt scheme is orders of magnitude faster than the explicit analog and allows for transparent interpretation of physical mechanisms. It is shown how the method can be expanded to multiscale modeling of aqueous salt solutions of many biomolecules with nonstatic charge distributions. Important examples are protein-protein aggregation, protein-polyelectrolyte complexation, and protein-membrane association.

Copolymer Synthesis and Characterization by Post-Polymerization Modification

NASA Astrophysics Data System (ADS)

Galvin, Casey James

This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in developing technologies that use SGPAs in aqueous environments, and point to a need for potential alternative grafting chemistries. The behavior of SGPAs in vapor environments remains an underexplored phenomenon. By changing systematically the chemistry of SGPAs derived from a parent sample, the influence of side chain functional groups on the swelling of weak and strong polyelectrolyte brushes in the presence of water, methanol and ethanol vapors is explored. The extent of swelling and solvent uptake depends strongly on the chemistry in the polymer side chain and of the solvent. Despite bearing a permanent electrostatic charge in the side chain, the strong polyelectrolyte brushes exhibit no behavior typical of polyelectrolytes in water due to no dissociation of the counterion. Of particular interest is the behavior in humid environments of an SGPA bearing a zwitterionic group in its side chain, which results in exposure of electrostatic charges without counterions. Using substrates bearing the aforementioned sigma gradient of polymeric grafts, evidence of inter- and intramolecular complex formation is presented. Finally, a method of developing SGPAs by polymerizing bulk polymer chains through surface-grafted monomers (SGMs) is described. The SGMs are incorporated onto a solid substrate using the same PPM reaction employed in the degrafting and vapor swelling experiments, highlighting the versatility of PPM. The thickness of these SGPAs is correlated to the bulk polymer chains MW, suggesting this technique can be used in existing industrial bulk polymerization processes.

Impact of magnetite nanoparticle incorporation on optical and electrical properties of nanocomposite LbL assemblies.

PubMed

Yashchenok, Alexey M; Gorin, Dmitry A; Badylevich, Mikhail; Serdobintsev, Alexey A; Bedard, Matthieu; Fedorenko, Yanina G; Khomutov, Gennady B; Grigoriev, Dmitri O; Möhwald, Helmuth

2010-09-21

Optical and electrical properties of polyelectrolyte/iron oxide nanocomposite planar films on silicon substrates were investigated for different amount of iron oxide nanoparticles incorporated in the films. The nanocomposite assemblies prepared by the layer-by-layer assembly technique were characterized by ellipsometry, atomic force microscopy, and secondary ion mass-spectrometry. Absorption spectra of the films reveal a shift of the optical absorption edge to higher energy when the number of deposited layers decreases. Capacitance-voltage and current-voltage measurements were applied to study the electrical properties of metal-oxide-semiconductor structures prepared by thermal evaporation of gold electrodes on nanocomposite films. The capacitance-voltage measurements show that the dielectric constant of the film increases with the number of deposited layers and the fixed charge and the trapped charge densities have a negative sign.

Encapsulation of Bacterial Spores in Nanoorganized Polyelectrolyte Shells (Postprint)

DTIC Science & Technology

2009-05-27

Nanoorganized polyelectrolyte shells have already found applica- tions in drug microencapsulation as a result of the tunable properties of the...polyelectrolyte shell.19 The same LbL technology allowed the introduction of enzymatic activity onto yeast cell shells in order to promote the conversion of

31 CFR 587.505 - Entries in certain accounts for normal service charges authorized.

Code of Federal Regulations, 2010 CFR

2010-07-01

... charges authorized. (a) A U.S. financial institution is authorized to debit any blocked account held at that financial institution in payment or reimbursement for normal service charges owed it by the owner of that blocked account. (b) As used in this section, the term normal service charge shall include...

Effect of the cross-linking agent on performances of NaCS-CS/WSC microcapsules.

PubMed

Wu, Qing-Xi; Xu, Xin; Wang, Zu-Li; Yao, Shan-Jing; Tong, Wang-Yu; Chen, Yan

2016-11-01

Based on the properties of oppositely charged natural polysaccharides, the polyelectrolyte complexes (PECs) prepared with chitosan-related polycationic polyelectrolytes and cellulose-related polyanionic polyelectrolytes have been widely concerned for their potential applications as micro-drug-carriers for colon. However, the poor mechanical property of the PECs becomes the obstacle encountered in practical applications. This study investigated the effect of the cross-linking agent (sodium polyphosphate, PPS) on the performances of sodium cellulose sulfate -chitosan/water soluble chitosan (NaCS-CS/WSC) microcapsules. The results revealed that PPS could penetrate through the PEC film and form tighter interior structures compared with the microcapsules without the addition of cross-linking agent. The NaCS-CS microcapsules and NaCS-WSC microcapsules with or without PPS had distinct microstructures, which could be ascribed to the different physicochemical properties of CS and WSC. During the formation process, CS can be dissolved in water under acidic conditions, while WSC can be directly dissolved and protonated in acid-free aqueous providing NH3(+) groups quickly, which resulted in the microstructure's difference. Further analysis showed the NaCS-CS-PPS microcapsules and NaCS-WSC-PPS microcapsules had lower swelling ratios due to their tighter interior microstructures that formed. The cross-linking agent had important effect on the total mass of PECs that produced; moreover, the decline of zeta potential of NaCS-CS-PPS microcapsules was lower than that of NaCS-CS microcapsules, similar trend was found in the NaCS-WSC-PPS microcapsules compared with NaCS-WSC microcapsules, indicating the PPS participated in the interactions and played a role in the microcapsules' formation process. Copyright © 2016 Elsevier B.V. All rights reserved.

Layer-by-Layer Assembly of Fluorine-Free Polyelectrolyte-Surfactant Complexes for the Fabrication of Self-Healing Superhydrophobic Films.

PubMed

Wu, Mengchun; An, Ni; Li, Yang; Sun, Junqi

2016-11-29

Fluorine-free self-healing superhydrophobic films are of significance for practical applications because of their extended service life and cost-effective and eco-friendly preparation process. In this study, we report the fabrication of fluorine-free self-healing superhydrophobic films by layer-by-layer (LbL) assembly of poly(sodium 4-styrenesulfonate) (PSS)-1-octadecylamine (ODA) complexes (PSS-ODA) and poly(allylamine hydrochloride) (PAH)-sodium dodecyl sulfonate (SDS) (PAH-SDS) complexes. The wettability of the LbL-assembled PSS-ODA/PAH-SDS films depends on the film structure and can be tailored by changing the NaCl concentration in aqueous dispersions of PSS-ODA complexes and the number of film deposition cycles. The freshly prepared PSS-ODA/PAH-SDS film with micro- and nanoscaled hierarchical structures is hydrophilic and gradually changes to superhydrophobic in air because the polyelectrolyte-complexed ODA and SDS surfactants tend to migrate to the film surface to cover the film with hydrophobic alkyl chains to lower its surface energy. The large amount of ODA and SDS surfactants loaded in the superhydrophobic PSS-ODA/PAH-SDS films and the autonomic migration of these surfactants to the film surface endow the resultant superhydrophobic films with an excellent self-healing ability to restore the damaged superhydrophobicity. The self-healing superhydrophobic PSS-ODA/PAH-SDS films are mechanically robust and can be deposited on various flat and nonflat substrates. The LbL assembly of oppositely charged polyelectrolyte-surfactant complexes provides a new way for the fabrication of fluorine-free self-healing superhydrophobic films with satisfactory mechanical stability, enhanced reliability, and extended service life.

Structure Formation in Salt-Free Solutions of Amphiphilic Sulfonated Polyelectrolytes

NASA Astrophysics Data System (ADS)

Bockstaller, Michael; Koehler, Werner

2000-03-01

Self-assembled systems have long attracted attention due to their practical importance in many technical and biological fields. Dodecyl-substituted poly(para-phenylen)sulfonates (abbreviated PPPS) are highly charged polyelectrolytes which in the uncharged state have been investigated extensively and an intrinsic persistence length of 15 nm has been reported. Due to their hydrophobic side chains, PPPS are compatible with water only as micellar aggregates and tend to form supramolecular structures even at concentrations as low as 10-5mol_mon.units/l. Because of the rodlike conformation of PPPS, this self-assembly leads to aggregates of anisotropic shape. Therefore, depolarized light scattering was employed to yield complementary information about structure and dynamics of these complex fluids. Aqueous solutions of PPPS at room temperature undergo a structural transition at a critical concentration of c_crit.=0.016 g/l. This transition is characterized by a strong increase of scattered intensity in forward direction and dynamic depolarized scattering. Above c_crit. the cylindrical micelles (L=310 nm, d=3.1 nm, N_radial=12) self assembly into large ellipsoidal clusters of size in the μ m range. Due to the strong increase of depolarized scattered intensity there has to be a preferential orientation of the micelles inside those clusters, which thus represent a lyotropic mesophase. By combining static and dynamic light scattering for the low q-range as well as small angle x-ray scattering for the higher q-range it is possible to determine size and shape of each aggregation step. Decreasing the molecular weight of the PPPS has profound influence on the micellar length and hence on c_crit. which is close to the overlap concentration (c ~ 1/L^3) allowing for the observation of the polyelectrolyte effect.

Selective Adsorption and Separation of Organic Dyes with Spherical Polyelectrolyte Brushes and Compressed Carbon Dioxide.

PubMed

Zhang, Rui; Yu, Zhenchuan; Wang, Lei; Shen, Qizhe; Hou, Xiaoyan; Guo, Xuhong; Wang, Junwei; Zhu, Xuedong; Yao, Yuan

2017-10-04

Dye-containing wastewater has caused serious environmental pollution. Herein, rationally designed spherical polyelectrolyte brushes (SPBs) with cationic charges, polystyrene-poly(2-aminoethylmethacrylate hydrochloride) (PS-PAEMH) as the absorbent, and compressed carbon dioxide as the antisolvent are proposed for the separation of the anionic dye eosin Y (EY) from a solution of mixed dyes. The adsorption behavior of EY onto PS-PAEMH was highly dependent on CO 2 pressure, contact time, and initial concentration. The maximum adsorption capacity of PS-PAEMH was 335.20 mg g -1 . FTIR and UV/Vis measurements proved that the electrostatic interactions between EY and PS-PAEMH played an important role in the absorbance process. The adsorption process fitted the pseudo-second-order kinetic model and Freundlich isotherm model very well. The combined dye and polymer brush could be easily separated through ion exchange by adding an aqueous solution of NaCl. Recovered PS-PAEMH retained a high adsorption capacity even after ten cycles of regeneration. This method provides a simple and effective way to separate ionic materials for environmental engineering. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic assessment of adsorptive fouling with the membranes modified via layer-by-layer self-assembly technique.

PubMed

Shen, Liguo; Cui, Xia; Yu, Genying; Li, Fengquan; Li, Liang; Feng, Shushu; Lin, Hongjun; Chen, Jianrong

2017-05-15

In this study, polyvinylidene fluoride (PVDF) microfiltration membrane was coated by dipping the membrane alternatingly in solutions of the polyelectrolytes (poly-diallyldimethylammonium chloride (PDADMAC) and polystyrenesulfonate (PSS)) via layer-by-layer (LBL) self-assembly technique to improve the membrane antifouling ability. Filtration experiments showed that, sludge cake layer on the coated membrane could be more easily washed off, and moreover, the remained flux ratio (RFR) of the coated membrane was obviously improved as compared with the control membrane. Characterization of the membranes showed that a polyelectrolyte layer was successfully coated on the membrane surfaces, and the hydrophilicity, surface charge and surface morphology of the coated membrane were changed. Based on the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) approaches, quantification of interfacial interactions between foulants and membranes in three different scenarios was achieved. It was revealed that there existed a repulsive energy barrier when a particle foulant adhered to membrane surface, and the enhanced electrostatic double layer (EL) interaction and energy barrier should be responsible for the improved antifouling ability of the coated membrane. This study provided a combined solution to membrane modification and interaction energy evaluation related with membrane fouling simultaneously. Copyright © 2017 Elsevier Inc. All rights reserved.

Mineral-Enhanced Polyacrylic Acid Hydrogel as an Oyster-Inspired Organic-Inorganic Hybrid Adhesive.

PubMed

Li, Ang; Jia, Yunfei; Sun, Shengtong; Xu, Yisheng; Minsky, Burcu Baykal; Stuart, M A Cohen; Cölfen, Helmut; von Klitzing, Regine; Guo, Xuhong

2018-03-28

Underwater adhesion is crucial to many marine life forms living a sedentary lifestyle. Amongst them, mussel adhesion has been mostly studied, which inspires numerous investigations of 3,4-dihydroxyphenylalanine (DOPA)-based organic adhesives. In contrast, reef-building oysters represent another important "inorganic" strategy of marine molluscs for adhesion by generating biomineralized organic-inorganic adhesives, which is still rarely studied and no synthetic analogues have ever been reported so far. Here, a novel type of oyster-inspired organic-inorganic adhesive based on a biomineralized polyelectrolyte hydrogel is reported, which consists of polyacrylic acid physically cross-linked by very small amorphous calcium carbonate nanoparticles (<3 nm). The mineral-enhanced polyelectrolyte hydrogel adhesive is shown to be injectable, reusable, and optically clear upon curing in air. Moreover, comparable adhesion performance to DOPA-based adhesives is found for the hydrogel adhesive in both dry and wet conditions, which can even be further enhanced by introducing a small amount of second large cross-linker such as negatively charged nanoparticles. The present mineral hydrogel represents a new type of bio-inspired organic-inorganic adhesive that may find a variety of potential applications in adhesive chemistry.

Chain conformation, rheological and charge properties of fucoidan extracted from sea cucumber Thelenota ananas: A semi-flexible coil negative polyelectrolyte.

PubMed

Xu, Xiaoqi; Xue, Changhu; Chang, Yaoguang; Liu, Guanchen

2017-12-15

As a bioactive and functional polysaccharide, sea cucumber fucoidan has received increasing attention. Chain conformation and physicochemical properties of fucoidan extracted from Thelenota ananas (Ta-FUC) was investigated by utilizing HPSEC-MALLS-Visc-RI, microelectrophoresis and steady shear measurements. The conformation parameter α s (0.61±0.02), the Mark-Houwink-Kuhn-Sakurada exponent α η (0.92±0.01), α h (0.64±0.01) and the Smidsrød-Haug stiffness parameter B (0.036±0.010) consistently manifested that Ta-FUC adopted a semi-flexible coil conformation in NaCl solution. Based on a wormlike cylinder model, stiffness parameters, including persistence length q (13.27±0.80nm) and cylinder diameter d (0.79nm), were calculated. This polysaccharide demonstrated shear-thinning rheological behaviour, and critical concentration from dilute to semidilute concentration regime was determined as 3.6mg/ml. Ta-FUC exhibited as a negative polyelectrolyte in wide pH and ionic strength ranges. These molecular characteristics and physicochemical properties would facilitate further application of Ta-FUC as a functional ingredient in food. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structure and interactions of human respiratory mucin

NASA Astrophysics Data System (ADS)

Purdy, Kirstin; Sheehan, John; Rubinstein, Michael; Wong, Gerard

2006-03-01

Human respiratory mucin plays a crucial role in the pathology of Cystic Fibrosis lung infections. Mucin is a flexible, linear polyelectrolyte, characterized by its many charged oligo-carbohydrate side chains that give it its bottle-brush structure. The macroscopic properties of a mucin suspension are known to change drastically with changes in ion concentration and solution pH, but little is known about the effect of these variables on individual mucin structure. We present preliminary results on the structural response of individual human respiratory mucin molecules to variations in concentration of ions of different valences via small angle x-ray diffraction.

A new route to prepare multiresponsive organogels from a block ionomer via charge-driven assembly.

PubMed

Zhang, Tao; Guo, Qipeng

2013-06-04

We report a novel route to prepare multiresponsive organogels through charge-driven assembly between a block ionomer and a diblock copolymer. The ionic complex aggregates to form spherical cores, which are connected by the middle block of the block ionomer to form gels. The organogels are responsive to acids, amines and salts.

Color tuning of photonic gel films by UV irradiation

NASA Astrophysics Data System (ADS)

Shin, Sung Eui; Kim, Su Young; Shin, Dong Myung

2010-02-01

Block copolymers have drawn increasing attention for fabricating functional nanomaterials due to their properties of self-assembly. In particular, photonic crystals hold promise for multiple optical applications. We prepared 1D photonic crystals with polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) lamellar films which is hydrophobic block-hydrophilic polyelectrolyte block polymer of 57 kg /mol-b-57 kg/mol. The lamellar stacks, which are alternating layers of hydrophilic and hydrophobic moiety of PS-b-P2VP, are obtained by exposing the spin coated film under chloroform vapor. The band gaps of the lamellar films interestingly varied after immersion into the quaternizing solvents containing 5wt% of iodomethane solubilized in n-hexane. We demonstrate about the influence of UV light on those photonic gel films. To study of different properties of films, UV-visible absorption spectra were measured as a different UV irradiation time at swollen films with distilled water. The UV-visible maximum absorption spectra shifted by UV irradiation time. Dependent on the time of UV irradiations, we can change the photonic band gap.

Band gap control using electric field of photonic gel cells fabricated with block copolymer and hydrogel.

PubMed

Lee, Sung Nam; Baek, Young Bin; Shin, Dong Myung

2014-08-01

Optical and electrical characteristics of the devices using photonic gel film and hydrogel electrolyte were studied. Poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) lamellar film with alternating hydrophobic block and hydrophilic polyelectrolyte block polymers (52 kg/mol-b-57 kg/mol) were prepared for the photonic gel. Poly(isobutylene-co-maleic acid) sodium salts were prepared for the hydrogel. This hydrogel fiber is common water swelling material and it owned ions for a device has conductivity. Photonic gel and hydrogel was spin coating onto Indium-tin-oxide (ITO) glass for make electric fields. The reflectance maximum wavelength of photonic crystal device shifted from 538 nm and reached to 557 nm, 585 nm and 604 nm during 30 min voltage applying time. The bandwidth variation was very limited. Loss of electrolyte was much less with hydrogel compared to the pure water. We can control color of hydrogel used photonic device by electric field with reasonable time range under moderate electric field by applying 2 V between two facing electrodes.

Lipophilic polyelectrolyte gel derived from phosphonium borate can absorb a wide range of organic solvents.

PubMed

Sunaga, Sokuro; Kokado, Kenta; Sada, Kazuki

2018-01-24

Herein, we demonstrate a polyelectrolyte gel which can absorb a wide range of organic solvents from dimethylsulfoxide (DMSO, permittivity: ε = 47.0) to tetrahydrofuran (ε = 5.6). The gel consists of polystyrene chains with small amounts (∼5 mol%) of lipophilic electrolytes derived from triphenylphosphonium tetraaryl borate. The swelling ability of the polyelectrolyte gel was higher than that of the alkyl ammonium tetraaryl borate previously reported by us, and this is attributed to the higher compatibility with organic solvents, as well as the higher dissociating ability, of the triphenyl phosphonium salt. The role of the ionic moieties was additionally confirmed by post modification of the polyelectrolyte gel via a conventional Wittig reaction, resulting in a nonionic gel. Our findings introduced here will lead to a clear-cut molecular design for polyelectrolyte gels which absorb all solvents.

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

NASA Technical Reports Server (NTRS)

Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

2002-01-01

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Polyelectrolyte Bundles: Finite size at thermodynamic equilibrium?

NASA Astrophysics Data System (ADS)

Sayar, Mehmet

2005-03-01

Experimental observation of finite size aggregates formed by polyelectrolytes such as DNA and F-actin, as well as synthetic polymers like poly(p-phenylene), has created a lot of attention in recent years. Here, bundle formation in rigid rod-like polyelectrolytes is studied via computer simulations. For the case of hydrophobically modified polyelectrolytes finite size bundles are observed even in the presence of only monovalent counterions. Furthermore, in the absence of a hydrophobic backbone, we have also observed formation of finite size aggregates via multivalent counterion condensation. The size distribution of such aggregates and the stability is analyzed in this study.

Molecular Building Block-Based Electronic Charges for High-Throughput Screening of Metal-Organic Frameworks for Adsorption Applications.

PubMed

Argueta, Edwin; Shaji, Jeena; Gopalan, Arun; Liao, Peilin; Snurr, Randall Q; Gómez-Gualdrón, Diego A

2018-01-09

Metal-organic frameworks (MOFs) are porous crystalline materials with attractive properties for gas separation and storage. Their remarkable tunability makes it possible to create millions of MOF variations but creates the need for fast material screening to identify promising structures. Computational high-throughput screening (HTS) is a possible solution, but its usefulness is tied to accurate predictions of MOF adsorption properties. Accurate adsorption simulations often require an accurate description of electrostatic interactions, which depend on the electronic charges of the MOF atoms. HTS-compatible methods to assign charges to MOF atoms need to accurately reproduce electrostatic potentials (ESPs) and be computationally affordable, but current methods present an unsatisfactory trade-off between computational cost and accuracy. We illustrate a method to assign charges to MOF atoms based on ab initio calculations on MOF molecular building blocks. A library of building blocks with built-in charges is thus created and used by an automated MOF construction code to create hundreds of MOFs with charges "inherited" from the constituent building blocks. The molecular building block-based (MBBB) charges are similar to REPEAT charges-which are charges that reproduce ESPs obtained from ab initio calculations on crystallographic unit cells of nanoporous crystals-and thus similar predictions of adsorption loadings, heats of adsorption, and Henry's constants are obtained with either method. The presented results indicate that the MBBB method to assign charges to MOF atoms is suitable for use in computational high-throughput screening of MOFs for applications that involve adsorption of molecules such as carbon dioxide.

Dynamics of Charged Species in Ionic-Neutral Block Copolymer and Surfactant Complexes [Structural Relaxation and Dynamics of Ionic-Neutral Block Copolymer Surfactant Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.

Structure–property relationships of ionic block copolymer (BCP) surfactant complexes are critical toward the progress of favorable engineering design of efficient charge-transport materials. In this paper, molecular dynamics simulations are used to understand the dynamics of charged-neutral BCP and surfactant complexes. The dynamics are examined for two different systems: charged-neutral double-hydrophilic and hydrophobic–hydrophilic block copolymers with oppositely charged surfactant moieties. The dynamics of the surfactant head, tails, and charges are studied for five different BCP volume fractions. We observe that the dynamics of the different species solely depend on the balance between electrostatic and entropic interactions between the charged species andmore » the neutral monomers. The favorable hydrophobic–hydrophobic interactions and the unfavorable hydrophobic–hydrophilic interactions determine the mobilities of the monomers. The dynamical properties of the charge species influence complex formation. Structural relaxations exhibit length-scale dependent behavior, with slower relaxation at the radius of gyration length-scale and faster relaxation at the segmental length-scale, consistent with previous results. The dynamical analysis correlates ion-exchange kinetics to the self-assembly behavior of the complexes.« less

Dynamics of Charged Species in Ionic-Neutral Block Copolymer and Surfactant Complexes [Structural Relaxation and Dynamics of Ionic-Neutral Block Copolymer Surfactant Complexes

DOE PAGES

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.; ...

2017-06-21

Structure–property relationships of ionic block copolymer (BCP) surfactant complexes are critical toward the progress of favorable engineering design of efficient charge-transport materials. In this paper, molecular dynamics simulations are used to understand the dynamics of charged-neutral BCP and surfactant complexes. The dynamics are examined for two different systems: charged-neutral double-hydrophilic and hydrophobic–hydrophilic block copolymers with oppositely charged surfactant moieties. The dynamics of the surfactant head, tails, and charges are studied for five different BCP volume fractions. We observe that the dynamics of the different species solely depend on the balance between electrostatic and entropic interactions between the charged species andmore » the neutral monomers. The favorable hydrophobic–hydrophobic interactions and the unfavorable hydrophobic–hydrophilic interactions determine the mobilities of the monomers. The dynamical properties of the charge species influence complex formation. Structural relaxations exhibit length-scale dependent behavior, with slower relaxation at the radius of gyration length-scale and faster relaxation at the segmental length-scale, consistent with previous results. The dynamical analysis correlates ion-exchange kinetics to the self-assembly behavior of the complexes.« less

Statistical crystallography of surface micelle spacing

NASA Technical Reports Server (NTRS)

Noever, David A.

1992-01-01

The aggregation of the recently reported surface micelles of block polyelectrolytes is analyzed using techniques of statistical crystallography. A polygonal lattice (Voronoi mosaic) connects center-to-center points, yielding statistical agreement with crystallographic predictions; Aboav-Weaire's law and Lewis's law are verified. This protocol supplements the standard analysis of surface micelles leading to aggregation number determination and, when compared to numerical simulations, allows further insight into the random partitioning of surface films. In particular, agreement with Lewis's law has been linked to the geometric packing requirements of filling two-dimensional space which compete with (or balance) physical forces such as interfacial tension, electrostatic repulsion, and van der Waals attraction.

Transition from capacitive coupling to direct charge transfer in asymmetric terahertz plasmonic assemblies.

PubMed

Ahmadivand, Arash; Sinha, Raju; Gerislioglu, Burak; Karabiyik, Mustafa; Pala, Nezih; Shur, Michael

2016-11-15

We experimentally and numerically analyze the charge transfer THz plasmons using an asymmetric plasmonic assembly of metallic V-shaped blocks. The asymmetric design of the blocks allows for the excitation of classical dipolar and multipolar modes due to the capacitive coupling. Introducing a conductive microdisk between the blocks, we facilitated the excitation of the charge transfer plasmons and studied their characteristics along with the capacitive coupling by varying the size of the disk.

Derivatizing weak polyelectrolytes--solution properties, self-aggregation, and association with anionic surfaces of hydrophobically modified poly(ethylene imine).

PubMed

Griffiths, Peter C; Paul, Alison; Fallis, Ian A; Wellappili, Champa; Murphy, Damien M; Jenkins, Robert; Waters, Sarah J; Nilmini, Renuka; Heenan, Richard K; King, Stephen M

2007-10-15

The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.

Conformation transitions of a single polyelectrolyte chain in a poor solvent: a replica-exchange lattice Monte-Carlo study.

PubMed

Wang, Lang; Wang, Zheng; Jiang, Run; Yin, Yuhua; Li, Baohui

2017-03-15

The thermodynamic behaviors of a strongly charged polyelectrolyte chain in a poor solvent are studied using replica-exchange Monte-Carlo simulations on a lattice model, focusing on the effects of finite chain length and the solvent quality on the chain conformation and conformation transitions. The neutralizing counterions and solvent molecules are considered explicitly. The thermodynamic quantities that vary continuously with temperature over a wide range are computed using the multiple histogram reweighting method. Our results suggest that the strength of the short-range hydrophobic interaction, the chain length, and the temperature of the system, characterized by ε, N, and T, respectively, are important parameters that control the conformations of a charged chain. When ε is moderate, the competition between the electrostatic energy and the short-range hydrophobic interaction leads to rich conformations and conformation transitions for a longer chain with a fixed length. Our results have unambiguously demonstrated the stability of the n-pearl-necklace structures, where n has a maximum value and decreases with decreasing temperature. The maximum n value increases with increasing chain length. Our results have also demonstrated the first-order nature of the conformation transitions between the m-pearl and the (m-1)-pearl necklaces. With the increase of ε, the transition temperature increases and the first-order feature becomes more pronounced. It is deduced that at the thermodynamic limit of infinitely long chain length, the conformational transitions between the m-pearl and the (m-1)-pearl necklaces may remain first order when ε > 0 and m = 2 or 3. Pearl-necklace conformations cannot be observed when either ε is too large or N is too small. To observe a pearl-necklace conformation, the T value needs to be carefully chosen for simulations performed at only a single temperature.

Poliovirus adsorption by 34 minerals and soils.

PubMed

Moore, R S; Taylor, D H; Sturman, L S; Reddy, M M; Fuhs, G W

1981-12-01

The adsorption of radiolabeled infectious poliovirus type 2 by 34 well-defined soils and mineral substrates was analyzed in a synthetic freshwater medium containing 1 mM CaCl(2) and 1.25 mM NaHCO(3) at pH 7. In a model system, adsorption of poliovirus by Ottawa sand was rapid and reached equilibrium within 1 h at 4 degrees C. Near saturation, the adsorption could be described by the Langmuir equation; the apparent surface saturation was 2.5 x 10(6) plaque-forming units of poliovirus per mg of Ottawa sand. At low surface coverage, adsorption was described by the Freundlich equation. The soils and minerals used ranged from acidic to basic and from high in organic content to organic free. The available negative surface charge on each substrate was measured by the adsorption of a cationic polyelectrolyte, polydiallyldimethylammonium chloride. Most of the substrates adsorbed more than 95% of the virus. In general, soils, in comparison with minerals, were weak adsorbents. Among the soils, muck and Genesee silt loam were the poorest adsorbents; among the minerals, montmorillonite, glauconite, and bituminous shale were the least effective. The most effective adsorbents were magnetite sand and hematite, which are predominantly oxides of iron. Correlation coefficients for substrate properties and virus adsorption revealed that the elemental composition of the adsorbents had little effect on poliovirus uptake. Substrate surface area and pH, by themselves, were not significantly correlated with poliovirus uptake. A strong negative correlation was found between poliovirus adsorption and both the contents of organic matter and the available negative surface charge on the substrates as determined by their capacities for adsorbing the cationic polyelectrolyte, polydiallyldimethylammonium chloride.

Effect of cationic polyelectrolytes on the performance of paper diagnostics for blood typing.

PubMed

McLiesh, Heather; Sharman, Scot; Garnier, Gil

2015-09-01

We investigated the effect that two common types of cationic polyelectrolytes used in papermaking might have on the performance of paper diagnostics using blood typing as an example. The results were analyzed in terms of red blood cells (RBC) retention and antibody-antigen specificity. Two questions were addressed: (1) can poly(amido-amine) epichlorohydrin (PAE) typically used for paper wet strength affect the diagnostic performance? (2) can high molecular weight cationic polyacrylamide (CPAM) employed as retention aid enhance or affect the selectivity and sensitivity of paper diagnostics? A series of paper varying in type of fibers and drying process were constructed with PAE and tested for blood typing performance. Residual PAE has no significant effect on blood typing paper diagnostics under normal conditions. Positives are unaffected with PAE, while negatives lose slight sharpness as some RBCs are unselectively retained. CPAM, the most common retention aid, can also be used to retain cells and biomolecules on paper. Paper towel was treated with CPAM solutions varying in polymer concentration and charge density and tested for blood typing. We found that CPAM dried on paper can retain RBC. CPAM affects the negative tests by retaining non-specifically individual RBC on fibers. RBC retention increases non-linearly with the CPAM charge density and concentration. As expected, wet CPAM retain RBCs at concentrations higher than 0.1wt%. As paper diagnostics are becoming a reality, more realistic papers than the Whatman filter paper will be engineered. This study provides guidance on how best use the required polymeric wet-strength and retention agents. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Synthetic and Biopolymer Gels - Similarities and Difference.

NASA Astrophysics Data System (ADS)

Horkay, Ferenc

2006-03-01

Ion exchange plays a central role in a variety of physiological processes, such as nerve excitation, muscle contraction and cell locomotion. Hydrogels can be used as model systems for identifying fundamental chemical and physical interactions that govern structure formation, phase transition, etc. in biopolymer systems. Polyelectrolyte gels are particularly well-suited to study ion-polymer interactions because their structure and physical-chemical properties (charge density, crosslink density, etc) can be carefully controlled. They are sensitive to different external stimuli such as temperature, ionic composition and pH. Surprisingly few investigations have been made on polyelectrolyte gels in salt solutions containing both monovalent and multivalent cations. We have developed an experimental approach that combines small angle neutron scattering and osmotic swelling pressure measurements. The osmotic pressure exerted on a macroscopic scale is a consequence of changes occurring at a molecular level. The intensity of the neutron scattering signal, which provides structural information as a function of spatial resolution, is directly related to the osmotic pressure. We have found a striking similarity in the scattering and osmotic behavior of polyacrylic acid gels and DNA gels swollen in nearly physiological salt solutions. Addition of calcium ions to both systems causes a sudden volume change. This volume transition, which occurs when the majority of the sodium counterions are replaced by calcium ions, is reversible. Such reversibility implies that the calcium ions are not strongly bound by the polyanion, but are free to move along the polymer chain, which allows these ions to form temporary bridges between negative charges on adjacent chains. Mechanical measurements reveal that the elastic modulus is practically unchanged in the calcium-containing gels, i.e., ion bridging is qualitatively different from covalent crosslinks.

Live celloidosome structures based on the assembly of individual cells by colloid interactions.

PubMed

Fakhrullin, Rawil F; Brandy, Marie-Laure; Cayre, Olivier J; Velev, Orlin D; Paunov, Vesselin N

2010-10-14

A new class of colloid structures, celloidosomes, has been developed which represent hollow microcapsules whose membranes consist of a single monolayer of living cells. Two routes for producing these structures were designed based on templating of: (i) air bubbles and (ii) anisotropic microcrystals of calcium carbonate with living cells, which allowed us to fabricate celloidosomes of spherical, rhombohedral and needle-like morphologies. Air microbubbles were templated by yeast cells coated with poly(allylamine hydrochloride) (PAH), then coated with carboxymethylcellulose and rehydrated resulting in the formation of spherical multicellular structures. Similarly, calcium carbonate microcrystals of anisotropic shapes were coated with several consecutive layers of oppositely charged polyelectrolytes to obtain a positive surface charge which was used to immobilise yeast cells coated with anionic polyelectrolyte of their surfaces. After dissolving of sacrificial cores, hollow multicellular structures were obtained. The viability of the cells in the produced structures was confirmed by using fluorescein diacetate. In order to optimize the separation of celloidosomes from free cells magnetic nanoparticles were immobilised onto the surface of templates prior to the cells deposition, which greatly facilitated the separation using a permanent magnet. Two alternative approaches were developed to form celloidosome structures using magnetically functionalised core-shell microparticles which resulted in the formation of celloidosomes with needle-like and cubic-like geometries which follows the original morphology of the calcium carbonate microcrystals. Our methods for fabrication of celloidosomes may found applications in the development of novel symbiotic bio-structures, artificial multicellular organisms and in tissue engineering. The unusual structure of celloidosomes resembles the primitive forms of multicellular species, like Volvox, and other algae and could be regarded as one possible mechanism of the evolutionary development of multicellularity.

Polyelectrolyte Complex Nanoparticles from Chitosan and Acylated Rapeseed Cruciferin Protein for Curcumin Delivery.

PubMed

Wang, Fengzhang; Yang, Yijie; Ju, Xingrong; Udenigwe, Chibuike C; He, Rong

2018-03-21

Curcumin is a polyphenol that exhibits several biological activities, but its low aqueous solubility results in low bioavailability. To improve curcumin bioavailability, this study has focused on developing a polyelectrolyte complexation method to form layer-by-layer assembled nanoparticles, for curcumin delivery, with positively charged chitosan (CS) and negatively charged acylated cruciferin (ACRU), a rapeseed globulin. Nanoparticles (NPs) were prepared from ACRU and CS (2:1) at pH 5.7. Three samples with weight of 5%, 10%, and 15% of curcumin, respectively, in ACRU/CS carrier were prepared. To verify the stability of the NPs, encapsulation efficiency and size of the 5% Cur-ACRU/CS NPs were determined at intervals of 5 days in a one month period. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, and differential scanning calorimetry confirmed the electrostatic interaction and hydrogen bond formation between the carrier and core. The result showed that hollow ACRU/CS nanocapsules (ACRU/CS NPs) and curcumin-loaded ACRU/CS nanoparticles (Cur-ACRU/CS NPs) were homogenized spherical with average sizes of 200-450 nm and zeta potential of +15 mV. Encapsulation and loading efficiencies were 72% and 5.4%, respectively. In vitro release study using simulated gastro (SGF) and intestinal fluids (SIF) showed controlled release of curcumin in 6 h of exposure. Additionally, the Cur-ACRU/CS NPs are nontoxic to cultured Caco-2 cells, and the permeability assay indicated that Cur-ACRU/CS NPs had improved permeability efficiency of free curcumin through the Caco-2 cell monolayer. The findings suggest that ACRU/CS NPs can be used for encapsulation and delivery of curcumin in functional foods.

Mesenchymal stem cell recruitment by stromal derived factor-1-delivery systems based on chitosan/poly(γ-glutamic acid) polyelectrolyte complexes.

PubMed

Gonçalves, Raquel M; Antunes, Joana C; Barbosa, Mário A

2012-04-10

Human mesenchymal stem cells (hMSCs) have an enormous potential for tissue engineering and cell-based therapies. With a potential of differentiation into multiple lineages and immune-suppression, these cells play a key role in tissue remodelling and regeneration. Here a method of hMSC recruitment is described, based on the incorporation of a chemokine in Chitosan (Ch)/Poly(γ-glutamic acid) (γ-PGA) complexes. Ch is a non-toxic, cationic polysaccharide widely investigated. γ-PGA is a hydrophilic, non-toxic, biodegradable and negatively charged poly-amino acid. Ch and γ-PGA, being oppositely charged, can be combined through electrostatic interactions. These biocompatible structures can be used as carriers for active substances and can be easily modulated in order to control the delivery of drugs, proteins, DNA, etc. Using the layer-by-layer method, Ch and γ-PGA were assembled into polyelectrolyte multilayers films (PEMs) with thickness of 120 nm. The chemokine stromal-derived factor-1 (SDF-1) was incorporated in these complexes and was continuously released during 120 h. The method of SDF-1 incorporation is of crucial importance for polymers assembly into PEMs and for the release kinetics of this chemokine. The Ch/γ-PGA PEMs with SDF-1 were able to recruit hMSCs, increasing the cell migration up to 6 fold to a maximum of 16.2 ± 4.9 cells/mm2. The controlled release of SDF-1 would be of great therapeutic value in the process of hMSC homing to injured tissues. This is the first study suggesting Ch/γ-PGA PEMs as SDF-1 reservoirs to recruit hMSCs, describing an efficient method of chemokine incorporation that allows a sustained released up to 5 days and that can be easily scaled-up.

Enzyme-polyelectrolyte complexes in water-ethanol mixtures: negatively charged groups artificially introduced into alpha-chymotrypsin provide additional activation and stabilization effects.

PubMed

Kudryashova, E V; Gladilin, A K; Vakurov, A V; Heitz, F; Levashov, A V; Mozhaev, V V

1997-07-20

Formation of noncovalent complexes between alpha-chymotrypsin (CT) and a polyelectrolyte, polybrene (PB), has been shown to produce two major effects on enzymatic reactions in binary mixtures of polar organic cosolvents with water. (i) At moderate concentrations of organic cosolvents (10% to 30% v/v), enzymatic activity of CT is higher than in aqueous solutions, and this activation effect is more significant for CT in complex with PB (5- to 7-fold) than for free enzyme (1.5- to 2.5-fold). (ii) The range of cosolvent concentrations that the enzyme tolerates without complete loss of catalytic activity is much broader. For enhancement of enzyme stability in the complex with the polycation, the number of negatively charged groups in the protein has been artificially increased by using chemical modification with pyromellitic and succinic anhydrides. Additional activation effect at moderate concentrations of ethanol and enhanced resistance of the enzyme toward inactivation at high concentrations of the organic solvent have been observed for the modified preparations of CT in the complex with PB as compared with an analogous complex of the native enzyme. Structural changes behind alterations in enzyme activity in water-ethanol mixtures have been studied by the method of circular dichroism (CD). Protein conformation of all CT preparations has not changed significantly up to 30% v/v of ethanol where activation effects in enzymatic catalysis were most pronounced. At higher concentrations of ethanol, structural changes in the protein have been observed for different forms of CT that were well correlated with a decrease in enzymatic activity. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 267-277, 1997.

Molecular Effects on Coacervate-Driven Block Copolymer Self Assembly

NASA Astrophysics Data System (ADS)

Lytle, Tyer; Radhakrishna, Mithun; Sing, Charles

Two oppositely charged polymers can undergo associative phase separation in a salt solution in a process known as \\x98complex coacervation. Recent work has used this as a motif to control the self-assembly behavior of a mixture of oppositely-charged block copolymers which form nanoscale structures. The materials formed from these complex coacervate-block copolymers (BCPs) have potential use as drug delivery systems, gels, and sensors. We have developed a hybrid Monte Carlo-Single Chain in a Mean Field (MC-SCMF) simulation method that is able to determine morphological phase diagrams for BCPs. This technique is an efficient way to calculate morphological phase diagrams and provides a clear link between molecular level features and self-assembly behaviors. Morphological phase diagrams showing the effects of polymer concentration, salt concentration, chain length, and charge-block fraction at large charge densities on self-assembly behavior have been determined. An unexpected phase transition from disorder to hexagonal packing at large salt concentrations has been observed for charge-block fractions equal to and larger than 0.5. This is attributed to the salt filling space stabilizing the morphology of the BCP.

Self-consistent treatment of the local dielectric permittivity and electrostatic potential in solution for polarizable macromolecular force fields.

PubMed

Hassan, Sergio A

2012-08-21

A self-consistent method is presented for the calculation of the local dielectric permittivity and electrostatic potential generated by a solute of arbitrary shape and charge distribution in a polar and polarizable liquid. The structure and dynamics behavior of the liquid at the solute/liquid interface determine the spatial variations of the density and the dielectric response. Emphasis here is on the treatment of the interface. The method is an extension of conventional methods used in continuum protein electrostatics, and can be used to estimate changes in the static dielectric response of the liquid as it adapts to charge redistribution within the solute. This is most relevant in the context of polarizable force fields, during electron structure optimization in quantum chemical calculations, or upon charge transfer. The method is computationally efficient and well suited for code parallelization, and can be used for on-the-fly calculations of the local permittivity in dynamics simulations of systems with large and heterogeneous charge distributions, such as proteins, nucleic acids, and polyelectrolytes. Numerical calculation of the system free energy is discussed for the general case of a liquid with field-dependent dielectric response.

Self-consistent treatment of the local dielectric permittivity and electrostatic potential in solution for polarizable macromolecular force fields

NASA Astrophysics Data System (ADS)

Hassan, Sergio A.

2012-08-01

A self-consistent method is presented for the calculation of the local dielectric permittivity and electrostatic potential generated by a solute of arbitrary shape and charge distribution in a polar and polarizable liquid. The structure and dynamics behavior of the liquid at the solute/liquid interface determine the spatial variations of the density and the dielectric response. Emphasis here is on the treatment of the interface. The method is an extension of conventional methods used in continuum protein electrostatics, and can be used to estimate changes in the static dielectric response of the liquid as it adapts to charge redistribution within the solute. This is most relevant in the context of polarizable force fields, during electron structure optimization in quantum chemical calculations, or upon charge transfer. The method is computationally efficient and well suited for code parallelization, and can be used for on-the-fly calculations of the local permittivity in dynamics simulations of systems with large and heterogeneous charge distributions, such as proteins, nucleic acids, and polyelectrolytes. Numerical calculation of the system free energy is discussed for the general case of a liquid with field-dependent dielectric response.

Self-consistent treatment of the local dielectric permittivity and electrostatic potential in solution for polarizable macromolecular force fields

PubMed Central

Hassan, Sergio A.

2012-01-01

A self-consistent method is presented for the calculation of the local dielectric permittivity and electrostatic potential generated by a solute of arbitrary shape and charge distribution in a polar and polarizable liquid. The structure and dynamics behavior of the liquid at the solute/liquid interface determine the spatial variations of the density and the dielectric response. Emphasis here is on the treatment of the interface. The method is an extension of conventional methods used in continuum protein electrostatics, and can be used to estimate changes in the static dielectric response of the liquid as it adapts to charge redistribution within the solute. This is most relevant in the context of polarizable force fields, during electron structure optimization in quantum chemical calculations, or upon charge transfer. The method is computationally efficient and well suited for code parallelization, and can be used for on-the-fly calculations of the local permittivity in dynamics simulations of systems with large and heterogeneous charge distributions, such as proteins, nucleic acids, and polyelectrolytes. Numerical calculation of the system free energy is discussed for the general case of a liquid with field-dependent dielectric response. PMID:22920098

Determining equilibrium osmolarity in poly(ethylene glycol)/chondrotin sulfate gels mimicking articular cartilage.

PubMed

Sircar, S; Aisenbrey, E; Bryant, S J; Bortz, D M

2015-01-07

We present an experimentally guided, multi-phase, multi-species polyelectrolyte gel model to make qualitative predictions on the equilibrium electro-chemical properties of articular cartilage. The mixture theory consists of two different types of polymers: poly(ethylene gylcol) (PEG), chondrotin sulfate (ChS), water (acting as solvent) and several different ions: H(+), Na(+), Cl(-). The polymer chains have covalent cross-links whose effect on the swelling kinetics is modeled via Doi rubber elasticity theory. Numerical studies on equilibrium polymer volume fraction and net osmolarity (difference in the solute concentration across the gel) show a complex interplay between ionic bath concentrations, pH, cross-link fraction and the average charge per monomer. Generally speaking, swelling is aided due to a higher average charge per monomer (or a higher particle fraction of ChS, the charged component of the polymer), low solute concentration in the bath, a high pH or a low cross-link fraction. A peculiar case arises at higher values of cross-link fraction, where it is observed that increasing the average charge per monomer leads to gel deswelling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Surface Tension Mediated Under-Water Adhesion of Rigid Spheres on Soft, Charged Surfaces

NASA Astrophysics Data System (ADS)

Sinha, Shayandev; Das, Siddhartha

2015-11-01

Understanding the phenomenon of surface-tension-mediated under-water adhesion is necessary for studying a plethora of physiological and technical phenomena, such as the uptake of bacteria or nanoparticle by cells, attachment of virus on bacterial surfaces, biofouling on large ocean vessels and marine devices, etc. This adhesion phenomenon becomes highly non-trivial in case the soft surface where the adhesion occurs is also charged. Here we propose a theory for analyzing such an under-water adhesion of a rigid sphere on a soft, charged surface, represented by a grafted polyelectrolyte layer (PEL). We develop a model based on the minimization of free energy that, in addition to considering the elastic and the surface-tension-mediated adhesion energies, also accounts for the PEL electric double layer (EDL) induced electrostatic energies. We show that in the presence of surface charges, adhesion gets enhanced. This can be explained by the fact that the increase in the elastic energy is better balanced by the lowering of the EDL energy associated with the adhesion process. The entire behaviour is further dictated by the surface tension components that govern the adhesion energy.

Molecular dynamics study of linear and comb-like polyelectrolytes in aqueous solution: effect of Ca2+ ions

NASA Astrophysics Data System (ADS)

Tong, Kefeng; Song, Xingfu; Sun, Shuying; Xu, Yanxia; Yu, Jianguo

2014-08-01

All-atom molecular dynamics simulations were employed to provide microscopic mechanism for the salt tolerance of polyelectrolytes dispersants. The conformational variation of polyelectrolytes and interactions between COO- groups and counterions/water molecules were also studied via radius of gyration and pair correlations functions. Sodium polyacrylate (NaPA) and sodium salts of poly(acrylic acid)-poly(ethylene oxide) (NaPA-PEO) were selected as the representative linear and comb-like polyelectrolyte, respectively. The results show that Ca2+ ions interact with COO- groups much stronger than Na+ ions and can bring ion-bridging interaction between intermolecular COO- groups in the NaPA systems. While in the NaPA-PEO systems, the introduced PEO side chains can prevent backbone chains from ion-bridging interactions and weaken the conformational changes. The present results can help in selecting and designing new-type efficient polyelectrolyte dispersants with good salt tolerance.

Fabrication of Thickness-Controllable Micropatterned Polyelectrolyte-Film/Nanoparticle Surfaces by Using the Plasma Oxidation Method.

PubMed

Zhu, Chun-Tao; Ma, Sheng-Hua; Zhang, Ying; Wang, Xue-Jing; Lv, Peng; Han, Xiao-Jun

2016-04-05

We have demonstrated a novel way to form thickness-controllable polyelectrolyte-film/nanoparticle patterns by using a plasma etching technique to form, first, a patterned self-assembled monolayer surface, followed by layer-by-layer assembly of polyelectrolyte-films/nanoparticles. Octadecyltrimethoxysilane (ODS) and (3-aminopropyl)triethoxysilane (APTES) self-assembled monolayers (SAMs) were used for polyelectrolyte-film and nanoparticle patterning, respectively. The resolution of the proposed patterning method can easily reach approximately 2.5 μm. The height of the groove structure was tunable from approximately 2.5 to 150 nm. The suspended lipid membrane across the grooves was fabricated by incubating the patterned polyelectrolyte groove arrays in solutions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) giant unilamellar vesicles (GUVs). The method demonstrated here reveals a new path to create patterned 2D or 3D structures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-Dimensional Bioprinting of Oppositely Charged Hydrogels with Super Strong Interface Bonding.

PubMed

Li, Huijun; Tan, Yu Jun; Liu, Sijun; Li, Lin

2018-04-04

A novel strategy to improve the adhesion between printed layers of three-dimensional (3D) printed constructs is developed by exploiting the interaction between two oppositely charged hydrogels. Three anionic hydrogels [alginate, xanthan, and κ-carrageenan (Kca)] and three cationic hydrogels [chitosan, gelatin, and gelatin methacrylate (GelMA)] are chosen to find the optimal combination of two oppositely charged hydrogels for the best 3D printability with strong interface bonding. Rheological properties and printability of the hydrogels, as well as structural integrity of printed constructs in cell culture medium, are studied as functions of polymer concentration and the combination of hydrogels. Kca2 (2 wt % Kca hydrogel) and GelMA10 (10 wt % GelMA hydrogel) are found to be the best combination of oppositely charged hydrogels for 3D printing. The interfacial bonding between a Kca layer and a GelMA layer is proven to be significantly higher than that of the bilayered Kca or bilayered GelMA because of the formation of polyelectrolyte complexes between the oppositely charged hydrogels. A good cell viability of >96% is obtained for the 3D-bioprinted Kca-GelMA construct. This novel strategy has a great potential for 3D bioprinting of layered constructs with a strong interface bonding.

Horseradish peroxidase-nanoclay hybrid particles of high functional and colloidal stability.

PubMed

Pavlovic, Marko; Rouster, Paul; Somosi, Zoltan; Szilagyi, Istvan

2018-08-15

Highly stable dispersions of enzyme-clay nanohybrids of excellent horseradish peroxidase activity were developed. Layered double hydroxide nanoclay was synthesized and functionalized with heparin polyelectrolyte to immobilize the horseradish peroxidase enzyme. The formation of a saturated heparin layer on the platelets led to charge inversion of the positively charged bare nanoclay and to highly stable aqueous dispersions. Great affinity of the enzyme to the surface modified platelets resulted in strong horseradish peroxidase adsorption through electrostatic and hydrophobic interactions as well as hydrogen bonding network and prevented enzyme leakage from the obtained material. The enzyme kept its functional integrity upon immobilization and showed excellent activity in decomposition of hydrogen peroxide and oxidation of an aromatic compound in the test reactions. In addition, remarkable long term functional stability of the enzyme-nanoclay hybrid was observed making the developed colloidal system a promising antioxidant candidate in biomedical treatments and industrial processes. Copyright © 2018 Elsevier Inc. All rights reserved.

Electrical manipulation of oligonucleotides grafted to charged surfaces.

PubMed

Rant, Ulrich; Arinaga, Kenji; Fujita, Shozo; Yokoyama, Naoki; Abstreiter, Gerhard; Tornow, Marc

2006-09-21

The electrical manipulation of short DNA molecules on surfaces offers novel functionalities with fascinating possibilities in the field of bio-interfaces. Here we present systematic investigations of the electrical interactions which govern the structure of oligonucleotides on charged gold surfaces. Successively, we address influences of the applied field strength, the role of DC electrode potentials, in particular for polycrystalline surfaces, as well as screening effects of the surrounding electrolyte solution. Data obtained for single and double stranded DNA exhibit differences which can be attributed to the dissimilar flexibility of the different molecular conformations. A comparison of the experimental results with a basic model shows how the alignment of the molecules adjusts according to a balance between electrically induced ordering and stochastic thermal motions. The presented conclusions are expected to be of general relevance for the behaviour of polyelectrolytes exposed to localized electric fields at interfaces.

Polyvinylpyrrolidone-sodium dodecylsulfate complex is a family of pseudo-polyanions with different charge densities: Evidence from capillary electrophoresis, capillary viscosimetry and conductometry.

PubMed

Wu, Yefan; Chen, Jie; Fang, Yun; Zhu, Meng

2016-10-01

Accordance with the previously supposed polyelectrolyte-like behaviour of neutral polymer-anionic surfactant complexes, direct evidence for the formation of the pseudo-polyanions in polyvinylpyrrolidone (PVP)-sodium dodecylsulfate (SDS) solution is put forward in this paper by capillary electrophoresis (CE) experiments in assistance with capillary viscosimetry and conductometry. The contradictory phenomena of the absolute value of relative electrophoretic mobility (re) increasing while the ionization degree (α) decreasing with the increasing specific clusterization [Г] in aqueous PVP-SDS solution are explained by the finding that the PVP-SDS complex is eventually a family of PVP-SDS pseudo-polyanions with different charge densities. And it is found countercations playing an important role in the formation of the PVP-SDS pseudo-polyanions in virtue of bridge effect. Copyright © 2016 Elsevier Inc. All rights reserved.

Concentration and Purification of Influenza Virus on Insoluble Polyelectrolytes

PubMed Central

Wallis, Craig; Homma, Akira; Melnick, Joseph L.

1972-01-01

A method for rapid concentration and purification of influenza virus by adsorption on and elution from an insoluble polyelectrolyte is described. To accomplish this task, influenza virus had to be rendered stable at pH 4 to 5, since viruses adsorb to the polyelectrolyte more efficiently at this pH range. A precipitate which forms in influenza harvests under acid conditions in the cold can be removed by ammonium sulfate at a concentration which traps the precipitate but not the virus. Thus, ammonium sulfate-treated influenza virus in allantoic fluid could be readily concentrated on the polyelectrolyte. Elution yielded a virus concentrate essentially free of nonviral proteins. PMID:4553141

Stability of polyelectrolyte-coated iron nanoparticles for T2-weighted magnetic resonance imaging

NASA Astrophysics Data System (ADS)

McGrath, Andrew J.; Dolan, Ciaran; Cheong, Soshan; Herman, David A. J.; Naysmith, Briar; Zong, Fangrong; Galvosas, Petrik; Farrand, Kathryn J.; Hermans, Ian F.; Brimble, Margaret; Williams, David E.; Jin, Jianyong; Tilley, Richard D.

2017-10-01

Iron nanoparticles are highly-effective magnetic nanoparticles for T2 magnetic resonance imaging (MRI). However, the stability of their magnetic properties is dependent on good protection of the iron core from oxidation in aqueous media. Here we report the synthesis of custom-synthesized phosphonate-grafted polyelectrolytes (PolyM3) of various chain lengths, for efficient coating of iron nanoparticles with a native iron oxide shell. The size of the nanoparticle-polyelectrolyte assemblies was investigated by transmission electron microscopy and dynamic light scattering, while surface attachment was confirmed by Fourier transform infrared spectroscopy. Low cytotoxicity was observed for each of the nanoparticle-polyelectrolyte ("Fe-PolyM3") assemblies, with good cell viability (>80%) remaining up to 100 μg mL-1 Fe in HeLa cells. When applied in T2-weighted MRI, corresponding T2 relaxivities (r2) of the Fe-PolyM3 assemblies were found to be dependent on the chain length of the polyelectrolyte. A significant increase in contrast was observed when polyelectrolyte chain length was increased from 6 to 65 repeating units, implying a critical chain length required for stabilization of the α-Fe nanoparticle core.

Self-assembly of model graft copolymers of agarose and weak polyelectrolyte-based amphiphilic diblock copolymers: controlled drug release and degradation.

PubMed

Muppalla, Ravikumar; Jewrajka, Suresh K; Prasad, Kamalesh

2013-06-01

Polysaccharide-based copolymers are promising biomaterials due to their biocompatibility and biodegradability. For potential biomedical applications the copolymer as a whole and all the degraded species must be biocompatible and easily removable from the system. In this regards, new model pH-responsive seaweed agarose (Agr) grafted with weak polyelectrolyte-based well-defined amphiphilic block copolymers ca. poly[(methyl methacrylate)-b-(2-dimethylamino)ethyl methacrylate)] (PMMA-b-PDMA) were designed and synthesized to study the self-assembly, degradation, and in vitro hydrophobic/hydrophilic drug release behavior. The graft copolymer solutions display extremely low critical micelle concentration (CMC) and form pH responsive stable micelles. The degradation study of the graft copolymer reveals that the entire degraded components are well soluble/dispersible in water due to formation of mixed micelles. The micelles are also strongly adsorbed on the mica surface owing to electrostatic interaction. One application of the graft copolymer micelles is that it can entrap both hydrophilic and poorly water soluble hydrophobic drugs effectively and exhibit slow release kinetics. The release kinetics of both the hydrophilic and poorly water soluble hydrophobic drugs change with pH as well as with the composition of the graft copolymer. Copyright © 2012 Wiley Periodicals, Inc.

A switchable polymer layer: Chain folding in end-charged polymer brushes

NASA Astrophysics Data System (ADS)

Heine, David; Wu, David T.

2001-03-01

We use a self-consistent field approximation to model the configurations of end-charged homopolymer and block copolymer brushes in response to an external electric field due to charges on the grafting surface. By varying the charge density on the grafting surface, we can cause the chains either to extend outward, greatly increasing the brush height, or to loop back to the grafting surface. We show that such a copolymer brush can present one block at the exposed surface in the extended state and present the other block in the retracted state. This occurs for both a solvated brush and a dry brush. We also compare these results to those of a modified Alexander-de Gennes model for the end-charged homopolymer brush.

Combined electroosmotically and pressure driven flow in soft nanofluidics.

PubMed

Matin, Meisam Habibi; Ohshima, Hiroyuki

2015-12-15

The present study is devoted to the analysis of mixed electroosmotic and pressure driven flows through a soft charged nanochannel considering boundary slip and constant charge density on the walls of the slit channel. The sources of the fluid flow are the pressure gradient along the channel axis and the electrokinetic effects that trigger an electroosmotic flow under the influence of a uniformly applied electric field. The polyelectrolyte layer (PEL) is denoted as a fixed charge layer (FCL) and the electrolyte ions can be present both inside and outside the PEL i.e., the PEL-electrolyte interface acts as a semi-penetrable membrane. The Poisson-Boltzmann equation is solved assuming the Debye-Hückel linearization for the low electric potential to provide us with analytical closed form solutions for the conservation equations. The conservation equations are solved to obtain the electric potential and velocity distributions in terms of governing dimensionless parameters. The results for the dimensionless electric potential, the dimensionless velocity and Poiseuille number are presented graphically and discussed in detail. Copyright © 2015 Elsevier Inc. All rights reserved.

Nanowires formed by the co-assembly of a negatively charged low-molecular weight gelator and a zwitterionic polythiophene.

PubMed

Li, Feng; Palaniswamy, Ganesan; de Jong, Menno R; Aslund, Andreas; Konradsson, Peter; Marcelis, Antonius T M; Sudhölter, Ernst J R; Stuart, Martien A Cohen; Leermakers, Frans A M

2010-06-21

Conjugated organic nanowires have been prepared by co-assembling a carboxylate containing low-molecular weight gelator (LMWG) and an amino acid substituted polythiophene derivative (PTT). Upon introducing the zwitterionic polyelectrolyte PTT to a basic molecular solution of the organogelator, the negative charges on the LMWG are compensated by the positive charges of the PTT. As a result, nanowires form through co-assembly. These nanowires are visualized by both transmission electron microscopy (TEM) and atomic force microscopy (AFM). Depending on the concentration and ratio of the components these nanowires can be micrometers long. These measurements further suggest that the aggregates adopt a helical conformation. The morphology of these nanowires are studied with fluorescent confocal laser scanning microscopy (CLSM). The interactions between LMWG and PTT are characterized by steady-state and time-resolved fluorescence spectroscopy studies. The steady-state spectra indicate that the backbone of the PTT adopts a more planar and more aggregated conformation when interacting with LMWG. The time- resolved fluorescence decay studies confirm this interpretation.

Surface chemistry of gold nanorods: origin of cell membrane damage and cytotoxicity

NASA Astrophysics Data System (ADS)

Wang, Liming; Jiang, Xiumei; Ji, Yinglu; Bai, Ru; Zhao, Yuliang; Wu, Xiaochun; Chen, Chunying

2013-08-01

We investigated how surface chemistry influences the interaction between gold nanorods (AuNRs) and cell membranes and the subsequent cytotoxicity arising from them in a serum-free cell culture system. Our results showed that the AuNRs coated with cetyl trimethylammonium bromide (CTAB) molecules can generate defects in the cell membrane and induce cell death, mainly due to the unique bilayer structure of CTAB molecules on the surface of the rods rather than their charge. Compared to CTAB-capped nanorods, positively charged polyelectrolyte-coated, i.e. poly(diallyldimethyl ammonium chloride) (PDDAC), AuNRs show improved biocompatibility towards cells. Thus, the present results indicate that the nature of surface molecules, especially their packing structures on the surface of AuNRs rather than surface charge, play a more crucial role in determining cytotoxicity. These findings about interfacial interactions could also explain the effects of internalized AuNRs on the structures or functions of organelles. This study will help understanding of the toxic nature of AuNRs and guide rational design of the surface chemistry of AuNRs for good biocompatibility in pharmaceutical therapy.

Acquisition of Infrared Variable Angle Spectroscopic Ellipsometer (IR-VASE)

DTIC Science & Technology

2016-04-22

External Advisory Board Meeting in Rio Piedras, PR. March 2016 Quiñonez B.*, Castilla D., Almodóvar J.; “ Polysaccharide -based polyelectrolyte...April 2016 Quiñonez B.*, Castilla D., Almodóvar J.; “ Polysaccharide -based polyelectrolyte multilayers: Physicochemical characterization and in...2016 Quiñonez B.*, Castilla D., Almodóvar J.; “ Polysaccharide -based polyelectrolyte multilayers: Physicochemical characterization and in vitro

Multilayer biomimetics: reversible covalent stabilization of a nanostructured biofilm.

PubMed

Li, Bingyun; Haynie, Donald T

2004-01-01

Designed polypeptides and electrostatic layer-by-layer self-assembly form the basis of promising research in bionanotechnology and medicine on development of polyelectrolyte multilayer films (PEMs). We show that PEMs can be formed from oppositely charged 32mers containing several cysteine residues. The polypeptides in PEMs become cross-linked under mild oxidizing conditions. This mimicking of disulfide (S-S) bond stabilization of folded protein structure confers on the PEMs a marked increase in resistance to film disassembly at acidic pH. The reversibility of S-S bond stabilization of PEMs presents further advantages for controlling physical properties of films, coatings, and other applications involving PEMs.

Length scale dependence of the dynamic properties of hyaluronic acid solutions in the presence of salt.

PubMed

Horkay, Ferenc; Falus, Peter; Hecht, Anne-Marie; Geissler, Erik

2010-12-02

In solutions of the charged semirigid biopolymer hyaluronic acid in salt-free conditions, the diffusion coefficient D(NSE) measured at high transfer momentum q by neutron spin echo is more than an order of magnitude smaller than that determined by dynamic light scattering, D(DLS). This behavior contrasts with neutral polymer solutions. With increasing salt content, D(DLS) approaches D(NSE), which is independent of ionic strength. Contrary to theoretical expectation, the ion-polymer coupling, which dominates the low q dynamics of polyelectrolyte solutions, already breaks down at distance scales greater than the Debye-Hückel length.

Formation of ion clusters in the phase separated structures of neutral-charged polymer blends

NASA Astrophysics Data System (ADS)

Kwon, Ha-Kyung; Olvera de La Cruz, Monica

2015-03-01

Polyelectrolyte blends, consisting of at least one charged species, are promising candidate materials for fuel cell membranes, for their mechanical stability and high selectivity for proton conduction. The phase behavior of the blends is important to understand, as this can significantly affect the performance of the device. The phase behavior is controlled by χN, the Flory-Huggins parameter multiplied by the number of mers, as well as the electrostatic interactions between the charged backbone and the counterions. It has recently been shown that local ionic correlations, incorporated via liquid state (LS) theory, enhance phase separation of the blend, even in the absence of polymer interactions. In this study, we show phase diagrams of neutral-charged polymer blends including ionic correlations via LS theory. In addition to enhanced phase separation at low χN, the blends show liquid-liquid phase separation at high electrostatic interaction strengths. Above the critical strength, the charged polymer phase separates into ion-rich and ion-poor regions, resulting in the formation of ion clusters within the charged polymer phase. This can be shown by the appearance of multiple spinodal and critical points, indicating the coexistence of several charge separated phases. This work was performed under the following financial assistance award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

Layer-by-Layer Assembled Nanotubes as Biomimetic Nanoreactors for Calcium Carbonate Deposition.

PubMed

He, Qiang; Möhwald, Helmuth; Li, Junbai

2009-09-17

Enzyme-loaded magnetic polyelectrolyte multilayer nanotubes prepared by layer-by-layer assembly combined with the porous template could be used as biomimetic nanoreactors. It is demonstrated that calcium carbonate can be biomimetically synthesized inside the cavities of the polyelectrolyte nanotubes by the catalysis of urease, and the size of the calcium carbonate precipitates was controlled by the cavity dimensions. The metastable structure of the calcium carbonate precipitates inside the nanotubes was protected by the outer shell of the polyelectrolyte multilayers. These features may allow polyelectrolyte nanotubes to be applied in the fields of nanomaterials synthesis, controlled release, and drug delivery. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Block of Brain Sodium Channels by Peptide Mimetics of the Isoleucine, Phenylalanine, and Methionine (IFM) Motif from the Inactivation Gate

PubMed Central

Eaholtz, Galen; Colvin, Anita; Leonard, Daniele; Taylor, Charles; Catterall, William A.

1999-01-01

Inactivation of sodium channels is thought to be mediated by an inactivation gate formed by the intracellular loop connecting domains III and IV. A hydrophobic motif containing the amino acid sequence isoleucine, phenylalanine, and methionine (IFM) is required for the inactivation process. Peptides containing the IFM motif, when applied to the cytoplasmic side of these channels, produce two types of block: fast block, which resembles the inactivation process, and slow, use-dependent block stimulated by strong depolarizing pulses. Fast block by the peptide ac-KIFMK-NH2, measured on sodium channels whose inactivation was slowed by the α-scorpion toxin from Leiurus quinquestriatus (LqTx), was reversed with a time constant of 0.9 ms upon repolarization. In contrast, control and LqTx-modified sodium channels were slower to recover from use-dependent block. For fast block, linear peptides of three to six amino acid residues containing the IFM motif and two positive charges were more effective than peptides with one positive charge, whereas uncharged IFM peptides were ineffective. Substitution of the IFM residues in the peptide ac-KIFMK-NH2 with smaller, less hydrophobic residues prevented fast block. The positively charged tripeptide IFM-NH2 did not cause appreciable fast block, but the divalent cation IFM-NH(CH2)2NH2 was as effective as the pentapeptide ac-KIFMK-NH2. The constrained peptide cyclic KIFMK containing two positive charges did not cause fast block. These results indicate that the position of the positive charges is unimportant, but flexibility or conformation of the IFM-containing peptide is important to allow fast block. Slow, use-dependent block was observed with IFM-containing peptides of three to six residues having one or two positive charges, but not with dipeptides or phenylalanine-amide. In contrast to its lack of fast block, cyclic KIFMK was an effective use-dependent blocker. Substitutions of amino acid residues in the tripeptide IFM-NH2 showed that large hydrophobic residues are preferred in all three positions for slow, use-dependent block. However, substitution of the large hydrophobic residue diphenylalanine or the constrained residues phenylglycine or tetrahydroisoquinoline for phe decreased potency, suggesting that this phe residue must be able to enter a restricted hydrophobic pocket during the binding of IFM peptides. Together, the results on fast block and slow, use-dependent block indicate that IFM peptides form two distinct complexes of different stability and structural specificity with receptor site(s) on the sodium channel. It is proposed that fast block represents binding of these peptides to the inactivation gate receptor, while slow, use-dependent block represents deeper binding of the IFM peptides in the pore. PMID:9925825

Cationic polyelectrolyte induced separation of some inorganic contaminants and their mixture (zirconium silicate, kaolin, K-feldspar, zinc oxide) as well as of the paraffin oil from water.

PubMed

Ghimici, Luminita

2016-03-15

The flocculation efficiency of a cationic polyelectrolyte with quaternary ammonium salt groups in the backbone, namely PCA5 was evaluated on zirconium silicate (kreutzonit), kaolin, K- feldspar and zinc oxide (ZnO) suspensions prepared either with each pollutant or with their mixture. The effect of several parameters such as settling time, polymer dose and the pollutant type on the separation efficacy was evaluated and followed by optical density and zeta potential measurements. Except for ZnO, the interactions between PCA5 and suspended particles led to low residual turbidity values (around 4% for kreutzonit, 5% for kaolin and 8% for K-feldspar) as well as to the reduction of flocs settling time (from 1200 min to 30 min and 120 min in case of kaolinit and K-feldspar, respectively), that meant a high efficiency in their separation. The negative value of the zeta potential and flocs size measurements, at the optimum polymer dose, point to contribution from charge patch mechanism for the particles flocculation. A good efficiency of PCA5 in separation of paraffin oil (a minimum residual turbidity of 9.8%) has been also found. Copyright © 2015 Elsevier Ltd. All rights reserved.

Mechanical properties of bulk graphene oxide/poly(acrylic acid)/poly(ethylenimine) ternary polyelectrolyte complex.

PubMed

Duan, Yipin; Wang, Chao; Zhao, Mengmeng; Vogt, Bryan D; Zacharia, Nicole S

2018-05-30

Ternary complexes formed in a single pot process through the mixing of cationic (branched polyethylenimine, BPEI) and anionic (graphene oxide, GO, and poly(acrylic acid), PAA) aqueous solutions exhibit superior mechanical performance in comparison to their binary analogs. The composition of the ternary complex can be simply tuned through the composition of the anionic solution, which influences the water content and mechanical properties of the complex. Increasing the PAA content in the complex decreases the overall water content due to improved charge compensation with the BPEI, but this change also significantly improves the toughness of the complex. Ternary complexes containing ≤32 wt% PAA were too brittle to generate samples for tensile measurements, while extension in excess of 250% could be reached with 57 wt% PAA. From this work, the influence of GO and PAA on the mechanical properties of GO/PAA/BPEI complexes were elucidated with GO sheets acting to restrain the viscous flow and improve the mechanical strength at low loading (<12.6 wt%) and PAA more efficiently complexes with BPEI than GO to generate a less swollen and stronger network. This combination overcomes the brittle nature of GO-BPEI complexes and viscous creep of PAA-BPEI complexes. Ternary nanocomposite complexes appear to provide an effective route to toughen and strengthen bulk polyelectrolyte complexes.

Proton conducting gel polyelectrolytes based on 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) copolymers with polyfunctional monomers. Part I. Anhydrous systems

NASA Astrophysics Data System (ADS)

Zygadło-Monikowska, Ewa; Florjańczyk, Zbigniew; Wielgus-Barry, Edyta; Paśniewski, Jarosław

The synthesis of crosslinked gel polyelectrolytes in polar aprotic solvents such as dimethylformamide (DMF) and a DMF and propylene carbonate (PC) mixture has been carried out in the copolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) and polyfunctional monomers. N, N‧-Methylene-bis-acrylamide, trioxyethylene dimethacrylate (M n ∼ 330) and trimethylolpropane ethoxylate (14/3 EO/OH) triacrylate were used as crosslinking monomers. The reactions were initiated thermally or by UV irradiation in the presence of Irgacure 184 or methyl benzoin ether. The crosslinking monomer was used in an amount of 0.5-13 wt.%. The effect of the type and concentration of the polyfunctional comonomer and type of solvent on the optical (color, transparency) and mechanical properties as well as the ability to conduct electrical charges have been studied. The application of a DMF and PC mixture enables to obtain transparent systems of good mechanical properties and high ambient temperature ionic conductivity of the order of 10 -3 to 10 -4 S cm -1, slightly lowered as compared with that of gels comprising DMF alone. The conducting properties of crosslinked gels have been compared with that of the AMPSA homopolymer solutions in analogous solvents.

Dendritic polyelectrolytes as seen by the Poisson-Boltzmann-Flory theory.

PubMed

Kłos, J S; Milewski, J

2018-06-20

G3-G9 dendritic polyelectrolytes accompanied by counterions are investigated using the Poisson-Boltzmann-Flory theory. Within this approach we solve numerically the Poisson-Boltzmann equation for the mean electrostatic potential and minimize the Poisson-Boltzmann-Flory free energy with respect to the size of the molecules. Such a scheme enables us to inspect the conformational and electrostatic properties of the dendrimers in equilibrium based on their response to varying the dendrimer generation. The calculations indicate that the G3-G6 dendrimers exist in the polyelectrolyte regime where absorption of counterions into the volume of the molecules is minor. Trapping of ions in the interior region becomes significant for the G7-G9 dendrimers and signals the emergence of the osmotic regime. We find that the behavior of the dendritic polyelectrolytes corresponds with the degree of ion trapping. In particular, in both regimes the polyelectrolytes are swollen as compared to their neutral counterparts and the expansion factor is maximal at the crossover generation G7.

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate)

PubMed Central

Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel

2016-01-01

Summary This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers. PMID:26977377

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate).

PubMed

Guzmán, Eduardo; Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel; Rubio, Ramón G

2016-01-01

This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers.

Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes

DOE PAGES

Mahalik, Jyoti P.; Yang, Yubo; Deodhar, Chaitra V.; ...

2016-03-06

Spatial dependencies of monomer volume fraction profiles of pH responsive polyelectrolyte brushes were investigated using field theories and neutron reflectivity experiments. In particular, planar polyelectrolyte brushes in good solvent were studied and direct comparisons between predictions of the theories and experimental measurements are presented. The comparisons between the theories and the experimental data reveal that solvent entropy and ion-pairs resulting from adsorption of counterions from the added salt play key roles in affecting the monomer distribution and must be taken into account in modeling polyelectrolyte brushes. Furthermore, the utility of this physics-based approach based on these theories for the predictionmore » and interpretation of neutron reflectivity profiles in the context of pH responsive planar polyelectrolyte brushes such as polybasic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and polyacidic poly(methacrylic acid) (PMAA) brushes is demonstrated. The approach provides a quantitative way of estimating molecular weights of the polymers polymerized using surface-initiated atom transfer radical polymerization.« less

Polystyrene-block-Poly(ionic liquid) Copolymers as Work Function Modifiers in Inverted Organic Photovoltaic Cells.

PubMed

Park, Jong Baek; Isik, Mehmet; Park, Hea Jung; Jung, In Hwan; Mecerreyes, David; Hwang, Do-Hoon

2018-02-07

Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO 2 ) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS 29 -b-PSImCl 60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.

31 CFR 540.504 - Entries in certain accounts for normal service charges authorized.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Statements of Licensing Policy § 540.504 Entries in certain accounts for normal service charges authorized. (a) A U.S. financial institution is authorized to debit any blocked account held by that financial institution in payment or reimbursement for normal service charges owed to it by the owner of the blocked...

Preparation and assessment of carboxylate polyelectrolyte as draw solute for forward osmosis.

PubMed

Cui, Hongtao; Zhang, Hanmin; Jiang, Wei; Yang, Fenglin

2018-02-01

Reverse draw solute diffusion not only reduces the water flux in forward osmosis (FO), but also contaminates the feed solution and eventually increases the regeneration cost of draw solution. In the present study, a new polyelectrolyte was synthesized as FO draw solute to address this problem. Acrylic acid and sodium p-styrenesulfonate monomers with hydrophilic group were used to fabricate carboxylate polyelectrolyte through free radical polymerization reaction. Results demonstrated that the osmotic pressure of carboxylate polyelectrolyte solution had a good linear relationship with concentration, and the viscosity of 0.18 g/mL solution was less than 5.4 cP. Active layer facing draw solution produced the initial water flux of 11.77 LMH and active layer facing feed solution yielded the initial water flux of 6.68 LMH when the concentration of draw solution was 0.18 g/mL. The reverse solute flux was around 1 gMH, and specific reverse solute flux of 0.18 g/mL carboxylate polyelectrolyte draw solution was 0.11 g/L which was much lower than that of traditional inorganic salts. Finally, diluted draw solution was regenerated via ultrafiltration, and the recovery efficiency of 94.78% was achieved. So, carboxylate polyelectrolyte can be suitable draw solute for FO.

Direct AFM force measurements between air bubbles in aqueous polydisperse sodium poly(styrene sulfonate) solutions: effect of collision speed, polyelectrolyte concentration and molar mass.

PubMed

Browne, Christine; Tabor, Rico F; Grieser, Franz; Dagastine, Raymond R

2015-07-01

Interactions between colliding air bubbles in aqueous solutions of polydisperse sodium poly(styrene sulfonate) (NaPSS) using direct force measurements were studied. The forces measured with deformable interfaces were shown to be more sensitive to the presence of the polyelectrolytes when compared to similar measurements using rigid interfaces. The experimental factors that were examined were NaPSS concentration, bubble collision velocity and polyelectrolyte molar mass. These measurements were then compared with an analytical model based on polyelectrolyte scaling theory in order to explain the effects of concentration and bubble deformation on the interaction between bubbles. Typically structural forces from the presence of monodisperse polyelectrolyte between interacting surfaces may be expected, however, it was found that the polydispersity in molar mass resulted in the structural forces to be smoothed and only a depletion interaction was able to be measured between interacting bubbles. It was found that an increase in number density of NaPSS molecules resulted in an increase in the magnitude of the depletion interaction. Conversely this interaction was overwhelmed by an increase in the fluid flow in the system at higher bubble collision velocities. Polymer molar mass dispersity plays a significant role in the interactions present between the bubbles and has implications that also affect the polyelectrolyte overlap concentration of the solution. Further understanding of these implications can be expected to play a role in the improvement in operations in such fields as water treatment and mineral processing where polyelectrolytes are used extensively. Copyright © 2015 Elsevier Inc. All rights reserved.

Adsorption of DNA to mica mediated by divalent counterions: a theoretical and experimental study.

PubMed

Pastré, David; Piétrement, Olivier; Fusil, Stéphane; Landousy, Fabrice; Jeusset, Josette; David, Marie-Odile; Hamon, Loïc; Le Cam, Eric; Zozime, Alain

2003-10-01

The adsorption of DNA molecules onto a flat mica surface is a necessary step to perform atomic force microscopy studies of DNA conformation and observe DNA-protein interactions in physiological environment. However, the phenomenon that pulls DNA molecules onto the surface is still not understood. This is a crucial issue because the DNA/surface interactions could affect the DNA biological functions. In this paper we develop a model that can explain the mechanism of the DNA adsorption onto mica. This model suggests that DNA attraction is due to the sharing of the DNA and mica counterions. The correlations between divalent counterions on both the negatively charged DNA and the mica surface can generate a net attraction force whereas the correlations between monovalent counterions are ineffective in the DNA attraction. DNA binding is then dependent on the fractional surface densities of the divalent and monovalent cations, which can compete for the mica surface and DNA neutralizations. In addition, the attraction can be enhanced when the mica has been pretreated by transition metal cations (Ni(2+), Zn(2+)). Mica pretreatment simultaneously enhances the DNA attraction and reduces the repulsive contribution due to the electrical double-layer force. We also perform end-to-end distance measurement of DNA chains to study the binding strength. The DNA binding strength appears to be constant for a fixed fractional surface density of the divalent cations at low ionic strength (I < 0.1 M) as predicted by the model. However, at higher ionic strength, the binding is weakened by the screening effect of the ions. Then, some equations were derived to describe the binding of a polyelectrolyte onto a charged surface. The electrostatic attraction due to the sharing of counterions is particularly effective if the polyelectrolyte and the surface have nearly the same surface charge density. This characteristic of the attraction force can explain the success of mica for performing single DNA molecule observation by AFM. In addition, we explain how a reversible binding of the DNA molecules can be obtained with a pretreated mica surface.

Virasoro conformal blocks and thermality from classical background fields

DOE PAGES

Fitzpatrick, A. Liam; Kaplan, Jared; Walters, Matthew T.

2015-11-30

We show that in 2d CFTs at large central charge, the coupling of the stress tensor to heavy operators can be re-absorbed by placing the CFT in a non-trivial background metric. This leads to a more precise computation of the Virasoro conformal blocks between heavy and light operators, which are shown to be equivalent to global conformal blocks evaluated in the new background. We also generalize to the case where the operators carry U(1) charges. The refined Virasoro blocks can be used as the seed for a new Virasoro block recursion relation expanded in the heavy-light limit. Furthermore, we commentmore » on the implications of our results for the universality of black hole thermality in AdS 3 , or equivalently, the eigenstate thermalization hypothesis for CFT 2 at large central charge.« less

Role of hydrodynamic interactions in dynamics of semi-flexible polyelectrolytes

NASA Astrophysics Data System (ADS)

Kekre, Rahul

Experiments have shown that DNA molecules in capillary electrophoresis migrate across field lines if a pressure gradient is applied simultaneously. We suggest that this migration results from an electrically driven flow field around the polyelectrolyte, which generates additional contributions to the center-of-mass velocity if the overall polymer conformation is asymmetric. Numerical simulations and experiments have demonstrated that confined polymers migrate towards the center of the channel in response to both external forces and uniaxial flows. Yet, migration towards the walls has been observed with combinations of external force and flow. In this work, the kinetic theory for an elastic dumbbell developed by Ma and Graham [Phys. Fluids 17, 083103 (2005)] has been extended to account for the effects of an external body force. Further modifications account for counterion screening within a Debye-Huckel approximation for the specific case of applied electric field. The theory qualitatively reproduces results of both experiments for the migration of neutral polymers and polyelectrolytes. The favorable comparison supports the contention [Long et al., Phys. Rev. Lett. 76, 3858 (1996)] that the hydrodynamic interactions in polyelectrolytes decay algebraically, as 1/r 3, rather than exponentially. A coarse-grained polymer model, without explicit charges, is developed and integrated using Brownian-dynamics simulations in analogy with the kinetic theory. The novel feature of the simulations is the inclusion of hydrodynamic interactions induced by the electric field. This model quantitatively captures experimental observations [Zheng and Yeung, Anal. Chem. 75, 3675 (2003)] of DNA migration under combined electric and pressure-driven flow fields in absence of any adjusted parameters. In addition the model predicts dependence of electrophoretic velocity on the instantaneous length of the polyelectrolyte which has been verified by experiments of Lee et. al. [Electrophoresis 31, 2813 (2010)]. The model also predicts phenomenons that are yet to be verified experimentally. These include decrease in diffusivity and increase in radius of gyration of the polyelectrolyte in high electric fields due to internal dispersion. The resulting change in orientation distribution at high electric fields decreases the extent of migration. Preliminary results from microfluidic experiments are presented in this dissertation demonstrating the saturation of migration. This dissertation also includes comparison of results from lattice-Boltzmann and Brownian dynamics simulations of a linear bead-spring model of DNA for two cases; infinite dilution and confinement. We have systematically varied the parameters that may affect the accuracy of the lattice-Boltzmann simulations, including grid resolution, temperature, polymer mass, periodic boundary size and fluid viscosity. For the case of a single chain Lattice-Boltzmann results for the diffusion coefficient and Rouse mode relaxation times were within 1--2% from those obtained from Brownian-dynamics. Results from both methods are also compared for polymer migration in confined flows driven by a uniform shear or pressure gradient. Center-of-mass distribution obtained from Lattice-Boltzmann simulations agrees quantitatively with Brownian-dynamics results, contradicting previously published results. The mobility matrix for a confined polymer was derived by applying Faxen's correction to the flow-field generated by a point force bounded by two parallel plates. This formulation of the mobility matrix is symmetric and positive-definite for all physically accessible configurations of the polymer.

Glucose Oxidase Adsorption on Sequential Adsorbed Polyelectrolyte Films Studied by Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Tristán, Ferdinando; Solís, Araceli; Palestino, Gabriela; Gergely, Csilla; Cuisinier, Frédéric; Pérez, Elías

2005-04-01

The adsorption of Glucose Oxidase (GOX) on layers of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) deposited on Sequentially Adsorbed Polyelectrolyte Films (SAPFs) were studied by three different spectroscopic techniques. These techniques are: Optical Wave Light Spectroscopy (OWLS) to measure surface density; Fluorescence Resonance Energy Transfer (FRET) to verify the adsorption of GOX on the surface; and Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection mode (FTIR-HATR) to inspect local structure of polyelectrolytes and GOX. Two positive and two negative polyelectrolytes are used: Cationic poly(ethyleneimine) (PEI) and poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrene sulfonate) (PSS) and poly(acrylic acid) (PAA). These spectroscopic techniques do not require any labeling for GOX or SAPFs, specifically GOX and PSS are naturally fluorescent and are used as a couple donor-acceptor for the FRET technique. The SAPFs are formed by a (PEI)-(PSS/PAH)2 film followed by (PAA/PAH)n bilayers. GOX is finally deposited on top of SAPFs at different values of n (n=1..5). Our results show that GOX is adsorbed on positive ended SAPFs forming a monolayer. Contrary, GOX adsorption is not observed on negative ended film polyelectrolyte. GOX stability was tested adding a positive and a negative polyelectrolyte after GOX adsorption. Protein is partially removed by PAH and PAA, with lesser force by PAA.

Direct optical imaging of nanoscale internal organization of polymer films

NASA Astrophysics Data System (ADS)

Suran, Swathi; Varma, Manoj

2018-02-01

Owing to its sensitivity and precise control at the nanoscale, polyelectrolytes have been immensely used to modify surfaces. Polyelectrolyte multilayers are generally water made and are easy to fabricate on any surface by the layer-by-layer (LbL) self-assembly process due to electrostatic interactions. Polyelectrolyte multilayers or PEMs can be assembled to form ultrathin membranes which can have potential applications in water filtration and desalination [1-3]. Hydration in PEMs is a consequence of both the bulk and surface phenomenon [4-7]. Bulk behavior of polymer membranes are well understood. Several techniques including reflectivity and contact angle measurements were used to measure the hydration in the bulk of polymer membranes [4, 8]. On the other hand their internal organization at the molecular level which can have a profound contribution in the transport mechanism, are not understood well. Previously, we engineered a technique, which we refer to as Bright-field Nanoscopy, which allows nanoscale optical imaging using local heterogeneities in a water-soluble germanium (Ge) thin film ( 25 nm thick) deposited on gold [8]. We use this technique to study the water transport in PEMs. It is understood that the surface charge and outer layers of the PEMs play a significant role in water transport through polymers [9-11]. This well-known `odd-even' effect arising on having different surface termination of the PEMs was optically observed with a spatial resolution unlike any other reported previously [12]. In this communication, we report that on increasing the etchant's concentration, one can control the lateral etching of the Ge film. This allowed the visualization of the nanoscale internal organization in the PEMs. Knowledge of the internal structure would allow one to engineer polymer membranes specific to applications such as drug delivering capsules, ion transport membranes and barriers etc. We also demonstrate a mathematical model involving a surface permeability term which captures the experimentally observed odd-even effect.

Divalent counterion-induced condensation of triple-strand DNA.

PubMed

Qiu, Xiangyun; Parsegian, V Adrian; Rau, Donald C

2010-12-14

Understanding and manipulation of the forces assembling DNA/RNA helices have broad implications for biology, medicine, and physics. One subject of significance is the attractive force between dsDNA mediated by polycations of valence ≥ 3. Despite extensive studies, the physical origin of the "like-charge attraction" remains unsettled among competing theories. Here we show that triple-strand DNA (tsDNA), a more highly charged helix than dsDNA, is precipitated by alkaline-earth divalent cations that are unable to condense dsDNA. We further show that our observation is general by examining several cations (Mg(2+), Ba(2+), and Ca(2+)) and two distinct tsDNA constructs. Cation-condensed tsDNA forms ordered hexagonal arrays that redissolve upon adding monovalent salts. Forces between tsDNA helices, measured by osmotic stress, follow the form of hydration forces observed with condensed dsDNA. Probing a well-defined system of point-like cations and tsDNAs with more evenly spaced helical charges, the counterintuitive observation that the more highly charged tsDNA (vs. dsDNA) is condensed by cations of lower valence provides new insights into theories of polyelectrolytes and the biological and pathological roles of tsDNA. Cations and tsDNAs also hold promise as a model system for future studies of DNA-DNA interactions and electrostatic interactions in general.

Electrokinetic flow in a capillary with a charge-regulating surface polymer layer.

PubMed

Keh, Huan J; Ding, Jau M

2003-07-15

An analytical study of the steady electrokinetic flow in a long uniform capillary tube or slit is presented. The inside wall of the capillary is covered by a layer of adsorbed or covalently bound charge-regulating polymer in equilibrium with the ambient electrolyte solution. In this solvent-permeable and ion-penetrable surface polyelectrolyte layer, ionogenic functional groups and frictional segments are assumed to distribute at uniform densities. The electrical potential and space charge density distributions in the cross section of the capillary are obtained by solving the linearized Poisson-Boltzmann equation. The fluid velocity profile due to the application of an electric field and a pressure gradient through the capillary is obtained from the analytical solution of a modified Navier-Stokes/Brinkman equation. Explicit formulas for the electroosmotic velocity, the average fluid velocity and electric current density on the cross section, and the streaming potential in the capillary are also derived. The results demonstrate that the direction of the electroosmotic flow and the magnitudes of the fluid velocity and electric current density are dominated by the fixed charge density inside the surface polymer layer, which is determined by the regulation characteristics such as the dissociation equilibrium constants of the ionogenic functional groups in the surface layer and the concentration of the potential-determining ions in the bulk solution.

Flexible Charged Macromolecules on Mixed Fluid Lipid Membranes: Theory and Monte Carlo Simulations

PubMed Central

Tzlil, Shelly; Ben-Shaul, Avinoam

2005-01-01

Fluid membranes containing charged lipids enhance binding of oppositely charged proteins by mobilizing these lipids into the interaction zone, overcoming the concomitant entropic losses due to lipid segregation and lower conformational freedom upon macromolecule adsorption. We study this energetic-entropic interplay using Monte Carlo simulations and theory. Our model system consists of a flexible cationic polyelectrolyte, interacting, via Debye-Hückel and short-ranged repulsive potentials, with membranes containing neutral lipids, 1% tetravalent, and 10% (or 1%) monovalent anionic lipids. Adsorption onto a fluid membrane is invariably stronger than to an equally charged frozen or uniform membrane. Although monovalent lipids may suffice for binding rigid macromolecules, polyvalent counter-lipids (e.g., phosphatidylinositol 4,5 bisphosphate), whose entropy loss upon localization is negligible, are crucial for binding flexible macromolecules, which lose conformational entropy upon adsorption. Extending Rosenbluth's Monte Carlo scheme we directly simulate polymer adsorption on fluid membranes. Yet, we argue that similar information could be derived from a biased superposition of quenched membrane simulations. Using a simple cell model we account for surface concentration effects, and show that the average adsorption probabilities on annealed and quenched membranes coincide at vanishing surface concentrations. We discuss the relevance of our model to the electrostatic-switch mechanism of, e.g., the myristoylated alanine-rich C kinase substrate protein. PMID:16126828

Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

NASA Astrophysics Data System (ADS)

Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

2011-03-01

The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

For Stimul-Responsive Polymers with Enhanced Efficiency in Reservoir Recovery Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charles McCormick; Roger Hester

Acrylamide-based hydrophobically modified (HM) polybetaines containing N-butylphenylacrylamide (BPAM) and varying amounts of either sulfobetaine (3-(2-acrylamido-2-methylpropanedimethylammonio)-1-propanesulfonate, AMPDAPS) or carboxybetaine (4-(2-acrylamido-2-methylpropyldimethylammonio) butanoate, AMPDAB) comonomers were synthesized via micellar copolymerization. The terpolymers were characterized via {sup 13}C NMR and UV spectroscopies, classical and dynamic light scattering, and potentiometric titration. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH, electrolyte concentration, and the addition of small molecule surfactants, was investigated using surface tension and rheological measurements. Low charge density terpolymers were found to show greater viscosity enhancement upon the addition of surfactant compared to the high charge densitymore » terpolymers. The addition of sodium dodecyl sulfate (SDS) produced the largest maximum in solution viscosity, while N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), N-dodecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-12), and Triton X-100 tended to show reduced viscosity enhancement. In most cases, the high charge density carboxybetaine terpolymer exhibited diminished solution viscosities upon surfactant addition. In our last report, we discussed solution thermodynamic theory that described changes in polymer coil conformation as a function of solution temperature and polymer molecular weight. These polymers contained no ionic charges. In this report, we expand polymer solution theory to account for the electrostatic interactions present in solutions of charged polymers. Polymers with ionic charges are referred to as polyions or polyelectrolytes.« less

A Comparative Study of Charges Made Through an Automated Circulation System in the Colorado State University Libraries.

ERIC Educational Resources Information Center

Burns, Robert W.

To determine use of portions of the collections at Colorado State University libraries and to identify heavily used sections, the collections were divided into 204 blocks according to Library of Congress classification letters. The number of charges made in each block was counted during a 1975 quarter for patrons, charges made to the reserve desk,…

Optoelectronic Properties of Conjugated Block Copolymer with Flexible Linking Group

NASA Astrophysics Data System (ADS)

Hu, Zhiqi; Verduzco, Rafael

State-of-the-art organic photovoltaics (OPVs) are prepared by depositing a disordered, co-continuous donor and acceptor blend. While optimization of material processing has produced significant improvements in performance, a fundamental understanding of charge separation and recombination at the donor/acceptor interface is lacking. Block copolymers with donor and acceptor polymer blocks provide an opportunity for controlling the donor-accepter interfacial structure and understanding its relationship to charge separation and photovoltaic performance. Here, we report the synthesis and characterization of donor-linker-acceptor block copolymers for use in OPVs. A series of poly(3-hexylthiophene)-block- poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (P3HT-linkerPFTBT) are synthesized with flexible oligo-ethylene glycol (PEG) linkers. Photoluminescence measurements demonstrate that the insertion of a non-conjugated linker has a significant impact on energy transfer between the two blocks, and the block copolymers are used as additives for bulk heterojunction OPVs. This work provides insight into the charge separation process and demonstrates a technique for tailoring the donor-accepter interface in OPVs.

Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength

PubMed Central

Sozanski, Krzysztof; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Sznajder, Anna; Holyst, Robert

2016-01-01

We investigate transport properties of model polyelectrolyte systems at physiological ionic strength (0.154 M). Covering a broad range of flow length scales—from diffusion of molecular probes to macroscopic viscous flow—we establish a single, continuous function describing the scale dependent viscosity of high-salt polyelectrolyte solutions. The data are consistent with the model developed previously for electrically neutral polymers in a good solvent. The presented approach merges the power-law scaling concepts of de Gennes with the idea of exponential length scale dependence of effective viscosity in complex liquids. The result is a simple and applicable description of transport properties of high-salt polyelectrolyte solutions at all length scales, valid for motion of single molecules as well as macroscopic flow of the complex liquid. PMID:27536866

Multilayer engineered nanoliposomes as a novel tool for oral delivery of lipopeptide-based vaccines against group A Streptococcus.

PubMed

Marasini, Nirmal; Giddam, Ashwini K; Ghaffar, Khairunnisa A; Batzloff, Michael R; Good, Michael F; Skwarczynski, Mariusz; Toth, Istvan

2016-05-01

To develop an oral nanovaccine delivery system for lipopeptide-based vaccine candidate against group A Streptococcus. Lipid-core peptide-1-loaded nanoliposomes were prepared as a template and coated with opposite-charged polyelectrolytes to produce particles with size <200 nm. Efficacy of this oral nanovaccine delivery system was evaluated in mice model. Polymer-coated liposomes produced significantly higher antigen-specific mucosal IgA and systemic IgG titers in comparison to vaccine formulated with a strong mucosal adjuvant upon oral immunization in mice. Moreover, high levels of systemic antibody titers were retained even at day 185 postprimary immunization. Efficient oral delivery platform for lipopeptide-based vaccines has been developed.

Influence of chitosan structure on the formation and stability of DNA-chitosan polyelectrolyte complexes.

PubMed

Strand, Sabina P; Danielsen, Signe; Christensen, Bjørn E; Vårum, Kjell M

2005-01-01

The interactions between DNA and chitosans varying in fractional content of acetylated units (FA), degree of polymerization (DP), and degree of ionization were investigated by several techniques, including an ethidium bromide (EtBr) fluorescence assay, gel retardation, atomic force microscopy, and dynamic and electrophoretic light scattering. The charge density of the chitosan and the number of charges per chain were found to be the dominating factors for the structure and stability of DNA-chitosan complexes. All high molecular weight chitosans condensed DNA into physically stable polyplexes; however, the properties of the complexes were strongly dependent on FA, and thereby the charge density of chitosan. By employing fully charged oligomers of constant charge density, it was shown that the complexation of DNA and stability of the polyplexes is governed by the number of cationic residues per chain. A minimum of 6-9 positive charges appeared necessary to provide interaction strength comparable to that of polycations. In contrast, further increase in the number of charges above 9 did not increase the apparent binding affinity as judged from the EtBr displacement assay. The chitosan oligomers exhibited a pH-dependent interaction with DNA, reflecting the number of ionized amino groups. The complexation of DNA and the stability of oligomer-based polyplexes became reduced above pH 7.4. Such pH-dependent dissociation of polyplexes around the physiological pH is highly relevant in gene delivery applications and might be one of the reasons for the high transfection activity of oligomer-based polyplexes observed.

Conjugated block copolymers as model materials to examine charge transfer in donor-acceptor systems

NASA Astrophysics Data System (ADS)

Gomez, Enrique; Aplan, Melissa; Lee, Youngmin

Weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. The lack of control of interfacial structure has also prevented studies of how driving forces promote charge photogeneration, leading to conflicting hypotheses in the organic photovoltaic literature. Our approach has focused on utilizing block copolymer architectures -where critical interfaces are controlled and stabilized by covalent bonds- to provide the hierarchical structure needed for high-performance organic electronics from self-assembled soft materials. For example, we have demonstrated control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers to achieve 3% power conversion efficiencies in non-fullerene photovoltaics. Furthermore, incorporating the donor-acceptor interface within the molecular structure facilitates studies of charge transfer processes. Conjugated block copolymers enable studies of the driving force needed for exciton dissociation to charge transfer states, which must be large to maximize charge photogeneration but must be minimized to prevent losses in photovoltage in solar cell devices. Our work has systematically varied the chemical structure, energetics, and dielectric constant to perturb charge transfer. As a consequence, we predict a minimum dielectric constant needed to minimize the driving force and therefore simultaneously maximize photocurrent and photovoltage in organic photovoltaic devices.

Mussel-inspired nano-building block assemblies for mimicking extracellular matrix microenvironments with multiple functions.

PubMed

Wang, Zhenming; Jia, Zhanrong; Jiang, Yanan; Li, Pengfei; Han, Lu; Lu, Xiong; Ren, Fuzeng; Wang, Kefeng; Yuan, Huiping

2017-08-03

The assembly of nano-building blocks is an effective way to produce artificial extracellular matrix microenvironments with hierarchical micro/nano structures. However, it is hard to assemble different types of nano-building blocks, to form composite coatings with multiple functions, by traditional layer-by-layer (LbL) self-assembly methods. Inspired by the mussel adhesion mechanism, we developed polydopamine (PDA)-decorated bovine serum albumin microspheres (BSA-MS) and nano-hydroxyapatite (nano-HA), and assembled them to form bioactive coatings with micro/nano structures encapsulating bone morphogenetic protein-2 (BMP-2). First, PDA-decorated nano-HA (nano-pHA) was obtained by oxidative polymerization of dopamine on nano-HA. Second, BMP-2-encapsulated BSA microspheres were prepared through desolvation, and then were also decorated by PDA (pBSA-MS). Finally, the nano-pHA and pBSA-MS were assembled using the adhesive properties of PDA. Bone marrow stromal cell cultures and in vivo implantation, showed that the pHA/pBSA (BMP-2) coatings can promote cell adhesion, proliferation, and benefited for osteoinductivity. PDA decoration was also applied to assemble various functional nanoparticles, such as nano-HA, polystyrene, and Fe 3 O 4 nanoparticles. In summary, this study provides a novel strategy for the assembly of biofunctional nano-building blocks, which surpasses traditional LbL self-assembly of polyelectrolytes, and can find broad applications in bioactive agents delivery or multi-functional coatings.

Measuring protein isoelectric points by AFM-based force spectroscopy using trace amounts of sample

NASA Astrophysics Data System (ADS)

Guo, Shifeng; Zhu, Xiaoying; Jańczewski, Dominik; Lee, Serina Siew Chen; He, Tao; Teo, Serena Lay Ming; Vancso, G. Julius

2016-09-01

Protein charge at various pH and isoelectric point (pI) values is important in understanding protein function. However, often only trace amounts of unknown proteins are available and pI measurements cannot be obtained using conventional methods. Here, we show a method based on the atomic force microscope (AFM) to determine pI using minute quantities of proteins. The protein of interest is immobilized on AFM colloidal probes and the adhesion force of the protein is measured against a positively and a negatively charged substrate made by layer-by-layer deposition of polyelectrolytes. From the AFM force-distance curves, pI values with an estimated accuracy of ±0.25 were obtained for bovine serum albumin, myoglobin, fibrinogen and ribonuclease A over a range of 4.7-9.8. Using this method, we show that the pI of the ‘footprint’ of the temporary adhesive proteins secreted by the barnacle cyprid larvae of Amphibalanus amphitrite is in the range 9.6-9.7.

Electrostatic effects on hyaluronic acid configuration

NASA Astrophysics Data System (ADS)

Berezney, John; Saleh, Omar

2015-03-01

In systems of polyelectrolytes, such as solutions of charged biopolymers, the electrostatic repulsion between charged monomers plays a dominant role in determining the molecular conformation. Altering the ionic strength of the solvent thus affects the structure of such a polymer. Capturing this electrostatically-driven structural dependence is important for understanding many biological systems. Here, we use single molecule manipulation experiments to collect force-extension behavior on hyaluronic acid (HA), a polyanion which is a major component of the extracellular matrix in all vertebrates. By measuring HA elasticity in a variety of salt conditions, we are able to directly assess the contribution of electrostatics to the chain's self-avoidance and local stiffness. Similar to recent results from our group on single-stranded nucleic acids, our data indicate that HA behaves as a swollen chain of electrostatic blobs, with blob size proportional to the solution Debye length. Our data indicate that the chain structure within the blob is not worm-like, likely due to long-range electrostatic interactions. We discuss potential models of this effect.

Cathodic electrodeposition of ceramic and organoceramic materials. Fundamental aspects.

PubMed

Zhitomirsky, I

2002-03-29

Electrodeposition of ceramic materials can be performed by electrophoretic (EPD) or electrolytic (ELD) deposition. Electrophoretic deposition is achieved via motion of charged particles towards an electrode under an applied electric field. Electrolytic deposition produces colloidal particles in cathodic reactions for subsequent deposition. Various electrochemical strategies and deposition mechanisms have been developed for electrodeposition of ceramic and organoceramic films, and are discussed in the present article. Electrode-position of ceramic and organoceramic materials includes mass transport, accumulation of particles near the electrode and their coagulation to form a cathodic deposit. Various types of interparticle forces that govern colloidal stability in the absence and presence of processing additives are discussed. Novel theoretical contributions towards an interpretation of particle coagulation near the electrode surface are reviewed. Background information is given on the methods of particle charging, stabilization of colloids in aqueous and non-aqueous media, electrophoretic mobility of ceramic particles and polyelectrolytes, and electrode reactions. This review also covers recent developments in the electrodeposition of ceramic and organoceramic materials.

Processes in suspensions of nanocomposite microcapsules exposed to external electric fields

NASA Astrophysics Data System (ADS)

Ermakov, A. V.; Lomova, M. V.; Kim, V. P.; Chumakov, A. S.; Gorbachev, I. A.; Gorin, D. A.; Glukhovskoy, E. G.

2016-04-01

Microcapsules with and without magnetite nanoparticles incorporated in the polyelectrolyte shell were prepared. The effect of external electric field on the nanocomposite polyelectrolyte microcapsules containing magnetite nanoparticles in the shell was studied in this work as a function of the electric field strength. Effect of electric fields on polyelectrolyte microcapsules and the control over integrity of polyelectrolyte microcapsules with and without inorganic nanoparticles by constant electric field has been investigated. Beads effect, aggregation and deformations of nanocomposite microcapsule shell in response to electric field were observed by confocal laser scanning microscopy (CLSM). Thus, a new approach for effect on the nanocomposite microcapsule, including opening microcapsule shell by an electric field, was demonstrated. These results can be used for creation of new systems for drug delivery systems with controllable release by external electric field.

Study of the micro-structural properties of RISUG--a newly developed male contraceptive.

PubMed

Kumar, Sunil; Roy, Sohini; Chaudhury, Koel; Sen, Prasenjit; Guha, Sujoy K

2008-07-01

A new male contraceptive given the name RISUG (an acronym for reversible inhibition of sperm under guidance) and presently undergoing advanced clinical trials has been developed. When injected into the lumen of the vas deferens, its polyelectrolytic nature induces a surface charge imbalance on sperm membrane system leading to the leakage of enzymes essential for fertilization. Contact mode atomic force microscopy (AFM) has been used to analyze quantitatively the micro-structural properties of RISUG and its precipitate in various systems. Hydrolysis of the contraceptive gel resulted in the formation of pores of varying dimensions. RISUG being a highly charged molecule, as evident from zeta potential measurements, has a tendency to form a complex with ionic biomolecules present in the seminal plasma. This is supported by the experimental observations using AFM. This RISUG-biomolecule complex possibly acts as an ionic trap for spermatozoa passing through the vas deferens. Micro-structural properties of RISUG including amplitude (root mean square, peak-to-valley distance, skewness and kurtosis) and spatial roughness have been studied to understand its response to various physiological conditions. Significant alterations in the surface charge distribution of the sperm cell is observed on exposure to RISUG. 2007 Wiley Periodicals, Inc.

Hidden Criticality of Counterion Condensation Near a Charged Cylinder.

PubMed

Cha, Minryeong; Yi, Juyeon; Kim, Yong Woon

2017-09-05

Counterion condensation onto a charged cylinder, known as the Manning transition, has received a great deal of attention since it is essential to understand the properties of polyelectrolytes in ionic solutions. However, the current understanding is still far from complete and poses a puzzling question: While the strong-coupling theory valid at large ionic correlations suggests a discontinuous nature of the counterion condensation, the mean-field theory always predicts a continuous transition at the same critical point. This naturally leads to a question how one can reconcile the mean-field theory with the strong-coupling prediction. Here, we study the counterion condensation transition on a charged cylinder via Monte Carlo simulations. Varying the cylinder radius systematically in relation to the system size, we find that in addition to the Manning transition, there exists a novel transition where all counterions are bound to the cylinder and the heat capacity shows a drop at a finite Manning parameter. A finite-size scaling analysis is carried out to confirm the criticality of the complete condensation transition, yielding the same critical exponents with the Manning transition. We show that the existence of the complete condensation is essential to explain how the condensation nature alters from continuous to discontinuous transition.

Engineering aqueous fiber assembly into silk-elastin-like protein polymers.

PubMed

Zeng, Like; Jiang, Linan; Teng, Weibing; Cappello, Joseph; Zohar, Yitshak; Wu, Xiaoyi

2014-07-01

Self-assembled peptide/protein nanofibers are valuable 1D building blocks for creating complex structures with designed properties and functions. It is reported that the self-assembly of silk-elastin-like protein polymers into nanofibers or globular aggregates in aqueous solutions can be modulated by tuning the temperature of the protein solutions, the size of the silk blocks, and the charge of the elastin blocks. A core-sheath model is proposed for nanofiber formation, with the silk blocks in the cores and the hydrated elastin blocks in the sheaths. The folding of the silk blocks into stable cores--affected by the size of the silk blocks and the charge of the elastin blocks--plays a critical role in the assembly of silk-elastin nanofibers. Furthermore, enhanced hydrophobic interactions between the elastin blocks at elevated temperatures greatly influence the nanoscale features of silk-elastin nanofibers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Ca2+ ion concentration on adsorption of poly(carboxylate ether)-based (PCE) superplasticizer on mica.

PubMed

Wu, Bo; Chun, Byong-Wa; Gu, Le; Kuhl, Tonya L

2018-05-09

Poly(carboxylate ether)-based (PCE) superplasticizers consist of a carboxylic acid backbone and grafted poly(ethylene glycol) (PEG) side chains. Ca 2+ ion bridging mechanism is commonly purported to control PCE's adsorption on negatively charged cement particle surfaces in cement suspension, thus PCE was expected to adsorb on negatively charged surfaces in synthetic pore solutions via Ca 2+ /COO - interactions. Adsorption behaviors of a commercial PCE on negatively charged mica were studied in aqueous electrolyte solutions by a surface forces apparatus. Direct force measurements indicated that the PCE adsorbed onto mica from 0.1 M K 2 SO 4 due to K + ion chelation by the ether oxygen units CH 2 CH 2 O on the PEG chains, but surprisingly did not adsorb from either 0.1 M K 2 SO 4 with saturated Ca(OH) 2 or 0.1 M Ca(NO 3 ) 2 . The adsorption in K 2 SO 4 was weak, enabling the adsorbed PCE layers to be squeezed out under modest compression. Upon separating the surfaces, the PCE immediately achieved an identical re-adsorption. In high-calcium conditions, the PCE was highly positively charged due to Ca 2+ ion chelation by PEG chains and backbone carboxylic groups COO - , and mica also underwent charge reversal due to electrostatic adsorption/binding of Ca 2+ ions. Consequently, the interaction between mica and PCE was electrostatically repulsive and no PCE adsorption occurred. These findings can be explained by the complex interplay of ion chelation by PEG chains, electrostatic binding and screening interactions with charged surfaces in the presence of monovalent and divalent counterions, and ultimately charge reversal of both the charged surfaces and polyelectrolyte in high divalent ion conditions. Copyright © 2018 Elsevier Inc. All rights reserved.

Electro-responsive polyelectrolyte-coated surfaces.

PubMed

Sénéchal, V; Saadaoui, H; Rodriguez-Hernandez, J; Drummond, C

2017-07-01

The anchoring of polymer chains at solid surfaces is an efficient way to modify interfacial properties like the stability and rheology of colloidal dispersions, lubrication and biocompatibility. Polyelectrolytes are good candidates for the building of smart materials, as the polyion chain conformation can often be tuned by manipulation of different physico-chemical variables. However, achieving efficient and reversible control of this process represents an important technological challenge. In this regard, the application of an external electrical stimulus on polyelectrolytes seems to be a convenient control strategy, for several reasons. First, it is relatively easy to apply an electric field to the material with adequate spatiotemporal control. In addition, in contrast to chemically induced changes, the molecular response to a changing electric field occurs relatively quickly. If the system is properly designed, this response can then be used to control the magnitude of surface properties. In this work we discuss the effect of an external electric field on the adhesion and lubrication properties of several polyelectrolyte-coated surfaces. The influence of the applied field is investigated at different pH and salt conditions, as the polyelectrolyte conformation is sensitive to these variables. We show that it is possible to fine tune friction and adhesion using relatively low applied fields.

Performance optimization of coagulant/flocculant in the treatment of wastewater from a beverage industry.

PubMed

Amuda, O S; Amoo, I A; Ajayi, O O

2006-02-28

This study investigated the effect of coagulation/flocculation treatment process on wastewater of Fumman Beverage Industry, Ibadan, Nigeria. The study also compared different dosages of coagulant, polyelectrolyte (non-ionic polyacrylamide) and different pH values of the coagulation processes. The effect of different dosages of polyelectrolyte in combination with coagulant was also studied. The results reveal that low pH values (3-8), enhance removal efficiency of the contaminants. Percentage removal of 78, 74 and 75 of COD, TSS and TP, respectively, were achieved by the addition of 500 mg/L Fe2(SO4)3.3H2O and 93, 94 and 96% removal of COD, TSS and TP, respectively, were achieved with the addition of 25 mg/L polyelectrolyte to the coagulation process. The volume of sludge produced, when coagulant was used solely, was higher compared to the use of polyelectrolyte combined with Fe2(SO4)3.3H2O. This may be as a result of non-ionic nature of the polyelectrolyte; hence, it does not chemically react with solids of the wastewater. Coagulation/flocculation may be useful as a pre-treatment process for beverage industrial wastewater prior to biological treatment.

Electrolyte-stimulated biphasic dissolution profile and stability enhancement for tablets containing drug-polyelectrolyte complexes.

PubMed

Kindermann, Christoph; Matthée, Karin; Sievert, Frank; Breitkreutz, Jörg

2012-10-01

Recently introduced drug-polyelectrolyte complexes prepared by hot-melt extrusion should be processed to solid dosage forms with tailor-made release properties. Their potential of stability enhancement should be investigated. Milled hot-melt extruded naproxen-EUDRAGIT® E PO polyelectrolyte complexes were subsequently processed to double-layer tablets with varying complex loadings on a rotary-die press. Physicochemical interactions were studied under ICH guideline conditions and using the Gordon-Taylor equation. Sorption and desorption were determined to investigate the influence of moisture and temperature on the complex and related to stability tests under accelerated conditions. Naproxen release from the drug-polyelectrolyte complex is triggered by electrolyte concentration. Depending on the complex loading, phosphate buffer pH 6.8 stimulated a biphasic dissolution profile of the produced double-layer tablets: immediate release from the first layer with 65% loading and prolonged release from the second layer within 24 h (98.5% loading). XRPD patterns proved pseudopolymorphism for tablets containing the pure drug under common storage conditions whereas the drug-complex was stable in the amorphous state. Drug-polyelectrolyte complexes enable tailor-made dissolution profiles of solid dosage forms by electrolyte stimulation and increase stability under common storage conditions.

Preparation of the polyelectrolyte complex hydrogel of biopolymers via a semi-dissolution acidification sol-gel transition method and its application in solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Jian; Chen, Yu; Yao, Ying; Tong, Zong-Rui; Li, Pu-Wang; Yang, Zi-Ming; Jin, Shao-Hua

2018-02-01

Hydrogels have drawn many attentions as the solid-state electrolytes in flexible solid-state supercapacitors (SCs) recently. Among them, the polyelectrolyte complex hydrogel (PECH) electrolytes of natural polymers are more competitive because of their environmentally friendly property and low cost. However, while mixing two biopolymer solutions with opposite charges, the strong electrostatic interactions between the cationic and anionic biopolymers may result in precipitates instead of hydrogels. Here we report a novel method, semi-dissolution acidification sol-gel transition (SD-A-SGT), for the preparation of the PECH of chitosan (CTS) and sodium alginate (SA), with the controllable sol-gel transition and uniform composition and successfully apply it as the hydrogel electrolyte of solid-state supercapacitors (SCs). The CTS-SA PECH exhibits an extremely high ionic conductivity of 0.051 S·cm-1 and reasonable mechanical properties with a tensile strength of 0.29 MPa and elongation at break of 109.5%. The solid-state SC fabricated with the CTS-SA PECH and conventional polyaniline (PANI) nanowire electrodes provided a high specific capacitance of 234.6 F·g-1 at 5 mV·s-1 and exhibited excellent cycling stability with 95.3% capacitance retention after 1000 cycles. Our work may pave a novel avenue to the preparation of biodegradable PECHs of full natural polymers, and promote the development of environmentally friendly electronic devices.

Release mechanism of doxazosin from carrageenan matrix tablets: Effect of ionic strength and addition of sodium dodecyl sulphate.

PubMed

Kos, Petra; Pavli, Matej; Baumgartner, Saša; Kogej, Ksenija

2017-08-30

The polyelectrolyte matrix tablets loaded with an oppositely charged drug exhibit complex drug-release mechanisms. In this study, the release mechanism of a cationic drug doxazosin mesylate (DM) from matrix tablets based on an anionic polyelectrolyte λ-carrageenan (λ-CARR) is investigated. The drug release rates from λ-CARR matrices are correlated with binding results based on potentiometric measurements using the DM ion-sensitive membrane electrode and with molecular characteristics of the DM-λ-CARR-complex particles through hydrodynamic size measurements. Experiments are performed in solutions with different ionic strength and with the addition of an anionic surfactant sodium dodecyl sulphate (SDS). It is demonstrated that in addition to swelling and erosion of tablets, the release rates depend strongly on cooperative interactions between DM and λ-CARR. Addition of SDS at concentrations below its critical micelle concentration (CMC) slows down the DM release through hydrophobic binding of SDS to the DM-λ-CARR complex. On the contrary, at concentrations above the CMC SDS pulls DM from the complex by forming mixed micelles with it and thus accelerates the release. Results involving SDS show that the concentration of surfactants that are naturally present in gastrointestinal environment may have a great impact on the drug release process. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raghuwanshi, Vikram Singh; Garusinghe, Uthpala Manavi; Ilavsky, Jan

Controlling nanoparticles (NPs) aggregation in cellulose/NPs composites allows to optimise NPs driven properties and their applications. Polyelectrolytes are used to control NPs aggregation and their retention within the fibrous matrix. Here in this study, we aim at evaluating how a polyelectrolyte (Cationic Polyacrylamide; CPAM, molecular weight: 13 MDa, charge: 50%, Radius of gyration: 30–36 nm) adsorbs and re-conforms onto the surface of silica(SiO 2) NPs differing in diameter (8, 22 and 74 nm) and to investigate the respective NPs aggregation in cellulose matrices. SEM shows the local area distribution of NPs in composites. Ultra-SAXS (USAXS) allows to evaluate the averagemore » NPs size distribution and the inter-particle interactions at length scale ranging from 1 to 1000 nm. USAXS data analysis reveals that CPAM covers multiple NPs of the smaller diameter (8 nm), presumably with a single chain to form large size NPs aggregates. As the NPs diameter is increased to 22 nm, CPAM re-conforms over NP surface forming a large shell of thickness 5.5 nm. For the composites with NPs of diameter 74 nm, the CPAM chain re-conforms further onto NP surface and the surrounding shell thickness decreases to 2.2 nm. Lastly, structure factor analysis reveals higher structural ordering for NPs as increases their diameter, which is caused by different conformations adopted by CPAM onto NPs surface.« less

Adsorption of mixtures of poly(amidoamine) dendrimers and sodium dodecyl sulfate at the air-water interface.

PubMed

Arteta, Marianna Yanez; Campbell, Richard A; Nylander, Tommy

2014-05-27

We relate the adsorption from mixtures of well-defined poly(amidoamine) (PAMAM) dendrimers of generations 4 and 8 with sodium dodecyl sulfate (SDS) at the air-water interface to the bulk solution properties. The anionic surfactant shows strong attractive interactions with the cationic dendrimers at pH 7, and electrophoretic mobility measurements indicate that the association is primarily driven by electrostatic interactions. Optical density measurements highlight the lack of colloidal stability of the formed bulk aggregates at compositions close to charge neutrality, the time scale of which is dependent on the dendrimer generation. Adsorption at the air-water interface was followed from samples immediately after mixing using a combination of surface tension, neutron reflectometry, and ellipsometry measurements. In the phase separation region for dendrimers of generation 4, we observed high surface tension corresponding to a depleted surfactant solution but only when the aggregates carried an excess of surfactant. Interestingly, these depleted adsorption layers contained spontaneously adsorbed macroscopic aggregates, and these embedded particles do not rearrange to spread monomeric material at the interface. These findings are discussed in relation to the interfacial properties of mixtures involving dendrimers of generation 8 as well as polydisperse linear and hyperbranched polyelectrolytes where there is polyelectrolyte bound to a surfactant monolayer. The results presented here demonstrate the capability of dendrimers to sequester anionic surfactants in a controllable manner, with potential applications as demulsification and antifoaming agents.

Phase Behavior of Salt-Free Polyelectrolyte Gel-Surfactant Systems.

PubMed

Andersson, Martin; Hansson, Per

2017-06-22

Ionic surfactants tend to collapse the outer parts of polyelectrolyte gels, forming shells that can be used to encapsulate other species including protein and peptide drugs. In this paper, the aqueous phase behavior of covalently cross-linked polyacrylate networks containing sodium ions and dodecyltrimethylammonium ions as counterions is investigated by means of swelling isotherms, dye staining, small-angle X-ray scattering, and confocal Raman spectroscopy. The equilibrium state is approached by letting the networks absorb pure water. With an increasing fraction of surfactant ions, the state of the water-saturated gels is found to change from being swollen and monophasic, via multiphasic states, to collapsed and monophasic. The multiphasic gels have a swollen, micelle-lean core surrounded by a collapsed, micelle-rich shell, or a collapsed phase forming a spheroidal inner shell separating two micelle-lean parts. It is shown that the transition between monophasic and core-shell states can be induced by variation of the osmotic pressure and variation of the charge of the micelles by forming mixed micelles with the nonionic surfactant octaethyleneglycol monododecylether. The experimental data are compared with theoretical predictions of a model derived earlier. In the calculations, the collapsed shell is assumed to be homogeneous, an approximation introduced here and shown to be excellent for a wide range of compositions. The theoretical results highlight the electrostatic and hydrophobic driving forces behind phase separation.

Polyelectrolyte-coated ion exchangers for cell-resistant expanded bed adsorption.

PubMed

Dainiak, Maria B; Galaev, Igor Yu; Mattiasson, Bo

2002-01-01

Adsorption chromatography in expanded beds is a widely used technology for direct capture of target proteins from fermentation broths. However, in many cases this method cannot be applied as a result of the strong tendency of cells or cell debris to interact with the adsorbent beads. To prevent contamination of the expanded bed with the biomass, STREAMLINE DEAE, anion exchanger designed for expanded bed adsorption, was modified with a layer of poly(acrylic acid) (PAA). The shielding layer of polyelectrolyte was attached to the surface of the matrix beads via electrostatic interactions. PAA with a high degree of polymerization was chosen to prevent diffusion of large polymer molecules into the pores of adsorbent. Thus, the shielding layer of PAA was adsorbed only at the mouth of the pores of STREAMLINE DEAE beads and only marginally decreased the binding capacity of the ion exchanger for bovine serum albumin, the model protein in this study. PAA-coated STREAMLINE DEAE practically did not interact with yeast cells, which otherwise bound strongly to the native adsorbent at neutral conditions. Cell-resistant PAA-coated anion exchanger was successfully used for isolation of BSA from the model protein mixture containing BSA, lysozyme (positively charged at applied conditions), and yeast cells. The layer of PAA was stable under mild elution conditions, and the modified adsorbent could be used in the repeated purification cycles.

Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Drozdov, A. D.; deClaville Christiansen, J.

2015-07-01

A constitutive model is developed for the elastic response of an anionic polyelectrolyte gel under swelling in water with an arbitrary pH and an arbitrary molar fraction of dissolved monovalent salt. A gel is treated as a three-phase medium consisting of a solid phase (polymer network), solvent (water), and solute (mobile ions). Transport of solvent and solute is thought of as their diffusion through the polymer network accelerated by an electric field formed by mobile and fixed ions and accompanied by chemical reactions (dissociation of functional groups attached to polymer chains and formation of ion pairs between bound charges and mobile counter-ions). Constitutive equations are derived by means of the free energy imbalance inequality for an arbitrary three-dimensional deformation with finite strains. These relations are applied to analyze equilibrium swelling diagrams on poly(acrylic acid) gel, poly(methacrylic acid) gel, and three composite hydrogels under water uptake in a bath (i) with a fixed molar fraction of salt and varied pH, and (ii) with a fixed pH and varied molar fraction of salt. To validate the ability of the model to predict observations quantitatively, material constants are found by matching swelling curves under one type of experimental conditions and results of simulation are compared with experimental data in the other type of tests.

Mechanically durable, superoleophobic coatings prepared by layer-by-layer technique for anti-smudge and oil-water separation

PubMed Central

Brown, Philip S.; Bhushan, Bharat

2015-01-01

Superoleophobic surfaces are of interest for anti-fouling, self-cleaning, anti-smudge, low-drag, anti-fog, and oil-water separation applications. Current bioinspired surfaces are of limited use due to a lack of mechanical durability. A so-called layer-by-layer approach, involving charged species with electrostatic interactions between layers, can provide the flexibility needed to improve adhesion to the substrate while providing a low surface tension coating at the air interface. In this work, a polyelectrolyte binder, SiO2 nanoparticles, and a fluorosurfactant are spray deposited separately to create a durable, superoleophobic coating. Polydiallyldimethylammonium chloride (PDDA) polyelectrolyte was complexed with a fluorosurfactant layer (FL), which provides oil repellency while being hydrophilic. This oleophobic/superhydrophilic behavior was enhanced through the use of roughening with SiO2 particles resulting in a superoleophobic coating with hexadecane contact angles exceeding 155° and tilt angles of less than 4°. The coating is also superhydrophilic, which is desirable for oil-water separation applications. The durability of these coatings was examined through the use of micro- and macrowear experiments. These coatings currently display characteristics of transparency. Fabrication of these coatings via the layer-by-layer technique results in superoleophobic surfaces displaying improved durability compared to existing work where either the durability or the oil-repellency is compromised. PMID:25731716

The Self-Assembly of Nanogold for Optical Metamaterials

NASA Astrophysics Data System (ADS)

Nidetz, Robert A.

2011-12-01

Optical metamaterials are an emerging field that enables manipulation of light like never before. Producing optical metamaterials requires sub-wavelength building blocks. The focus here was to develop methods to produce building blocks for metamaterials from nanogold. Electron-beam lithography was used to define an aminosilane patterned chemical template in order to electrostatically self-assemble citrate-capped gold nanoparticles. Equilibrium self-assembly was achieved in 20 minutes by immersing chemical templates into gold nanoparticle solutions. The number of nanoparticles that self-assembled on an aminosilane dot was controlled by manipulating the diameters of the dots and nanoparticles. Adding salt to the nanoparticle solution enabled the nanoparticles to self-assemble in greater numbers on the same sized dot. However, the preparation of the nanoparticle solution containing salt was sensitive to spikes in the salt concentration which led to aggregation of the nanoparticles and non-specific deposition. Gold nanorods were also electrostatically self-assembled. Polyelectrolyte-coated gold nanorods were patterned with limited success. A polyelectrolyte chemical template also patterned gold nanorods, but the gold nanorods preferred to pattern on the edges of the pattern. Ligand-exchanged gold nanorods displayed the best self-assembly, but suffered from slow kinetics. Self-assembled gold nanoparticles were cross-linked with poly(diallyldimethylammonium chloride). The poly(diallyldimethylammonium chloride) allowed additional nanoparticles to pattern on top of the already patterned nanoparticles. Cross-linked nanoparticles were lifted-off of the substrate by sonication in a sodium hydroxide solution. The presence of van der Waals forces and/or amine bonding prevent the nanogold from lifting-off without sonication. A good-solvent evaporation process was used to self-assemble poly(styrene) coated gold nanoparticles into spherical microbead assemblies. The use of larger nanoparticles and larger poly(styrene) ligands resulted in larger and smaller assemblies, respectively. Stirring the solution resulted in a wider size distribution of microbead assemblies due to the stirring's shear forces. Two undeveloped methods to self-assemble nanogold were investigated. One method used block-copolymer thin films as chemical templates to direct the electrostatic self-assembly of nanogold. Another method used gold nanorods that are passivated with different ligands on different faces. The stability of an alkanethiol ligand in different acids and bases was investigated to determine which materials could be used to produce Janus nanorods.

Narrow Band Gap Conjugated Polyelectrolytes.

PubMed

Cui, Qiuhong; Bazan, Guillermo C

2018-01-16

Two essential structural elements define a class of materials called conjugated polyelectrolytes (CPEs). The first is a polymer framework with an electronically delocalized, π-conjugated structure. This component allows one to adjust desirable optical and electronic properties, for example the range of wavelengths absorbed, emission quantum yields, electron affinity, and ionization potential. The second defining feature is the presence of ionic functionalities, which are usually linked via tethers that can modulate the distance of the charged groups relative to the backbone. These ionic groups render CPEs distinct relative to their neutral conjugated polymer counterparts. Solubility in polar solvents, including aqueous media, is an immediately obvious difference. This feature has enabled the development of optically amplified biosensor protocols and the fabrication of multilayer organic semiconductor devices through deposition techniques using solvents with orthogonal properties. Important but less obvious potential advantages must also be considered. For example, CPE layers have been used to introduce interfacial dipoles and thus modify the effective work function of adjacent electrodes. One can thereby modulate the barriers for charge injection into semiconductor layers and improve the device efficiencies of organic light-emitting diodes and solar cells. With a hydrophobic backbone and hydrophilic ionic sites, CPEs can also be used as dispersants for insoluble materials. Narrow band gap CPEs (NBGCPEs) have been studied only recently. They contain backbones that comprise electron-rich and electron-poor fragments, a combination that leads to intramolecular charge transfer excited states and enables facile oxidation and reduction. One particularly interesting combination is NBGCPEs with anionic sulfonate side groups, for which spontaneous self-doping in aqueous media is observed. That no such doping is observed with cationic NBGCPEs indicates that the interplay between electrostatic forces and the redox chemistry of the organic semiconducting chain is essential for stabilizing the polaronic states and increasing the conductivity of the bulk. Capitalizing upon the properties of NBGCPEs has resulted in a range of new applications. When doped, they can be introduced as interlayers in organic and perovskite solar cells. Single-walled carbon nanotubes can be n- or p-doped with NBGCPEs, depending on whether the same backbone contains attached cationic or anionic side groups, respectively. The resulting dispersions can be used to fabricate flexible thermoelectric devices in which the n- and p-semiconductor legs are nearly identical in terms of chemical composition. Electrostatic interactions with negatively charged cell walls, in combination with the long-wavelength absorption and high photothermal efficiencies, have been used to create effective agents for photothermal killing of bacteria. Additionally, recent results have shown that cationic NBGCPEs can effectively n-dope graphene and that this doping is temperature-dependent. The preferential charge carriers can therefore be chosen to be electrons or holes depending on the applied temperature.

Conjugated-polyelectrolyte-grafted cotton fibers act as "micro flypaper" for the removal and destruction of bacteria.

PubMed

Ista, Linnea K; Dascier, Dimitri; Ji, Eunkyung; Parthasarathy, Anand; Corbitt, Thomas S; Schanze, Kirk S; Whitten, David G

2011-08-01

We demonstrate herein a method for chemically modifying cotton fibers and cotton-containing fabric with a light-activated, cationic phenylene-ethynylene (PPE-DABCO) conjugated polyelectrolyte biocide. When challenged with Pseudomonas aeruginosa and Bacillus atropheaus vegetative cells from liquid suspension, light-activated PPE-DABCO effects 1.2 and 8 log, respectively, losses in viability of the exposed bacteria. These results suggest that conjugated polyelectrolytes retain their activity when grafted to fabrics, showing promise for use in settings where antimicrobial textiles are needed.

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

PubMed

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Molecular simulation of the swelling of polyelectrolyte gels by monovalent and divalent counterions

PubMed Central

Yin, De-Wei; Horkay, Ferenc; Douglas, Jack F.; de Pablo, Juan J.

2008-01-01

Permanently crosslinked polyelectrolyte gels are known to undergo discontinuous first-order volume phase transitions, the onset of which may be caused by a number of factors. In this study we examine the volumetric properties of such polyelectrolyte gels in relation to the progressive substitution of monovalent counterions by divalent counterions as the gels are equilibrated in solvents of different dielectric qualities. We compare the results of coarse-grained molecular dynamics simulations of polyelectrolyte gels with previous experimental measurements by others on polyacrylate gels. The simulations show that under equilibrium conditions there is an approximate cancellation between the electrostatic contribution and the counterion excluded-volume contribution to the osmotic pressure in the gel-solvent system; these two contributions to the osmotic pressure have, respectively, energetic and entropic origins. The finding of such a cancellation between the two contributions to the osmotic pressure of the gel-solvent system is consistent with experimental observations that the swelling behavior of polyelectrolyte gels can be described by equations of state for neutral gels. Based on these results, we show and explain that a modified form of the Flory–Huggins model for nonionic polymer solutions, which accounts for neither electrostatic effects nor counterion excluded-volume effects, fits both experimental and simulated data for polyelectrolyte gels. The Flory–Huggins interaction parameters obtained from regression to the simulation data are characteristic of ideal polymer solutions, whereas the experimentally obtained interaction parameters, particularly that associated with the third virial coefficient, exhibit a significant departure from ideality, leading us to conclude that further enhancements to the simulation model, such as the inclusion of excess salt, the allowance for size asymmetric electrolytes, or the use of a distance-dependent solvent dielectricity model, may be required. Molecular simulations also reveal that the condensation of divalent counterions onto the polyelectrolyte network backbone occurs preferentially over that of monovalent counterions. PMID:19045224

Molecular simulation of the swelling of polyelectrolyte gels by monovalent and divalent counterions.

PubMed

Yin, De-Wei; Horkay, Ferenc; Douglas, Jack F; de Pablo, Juan J

2008-10-21

Permanently crosslinked polyelectrolyte gels are known to undergo discontinuous first-order volume phase transitions, the onset of which may be caused by a number of factors. In this study we examine the volumetric properties of such polyelectrolyte gels in relation to the progressive substitution of monovalent counterions by divalent counterions as the gels are equilibrated in solvents of different dielectric qualities. We compare the results of coarse-grained molecular dynamics simulations of polyelectrolyte gels with previous experimental measurements by others on polyacrylate gels. The simulations show that under equilibrium conditions there is an approximate cancellation between the electrostatic contribution and the counterion excluded-volume contribution to the osmotic pressure in the gel-solvent system; these two contributions to the osmotic pressure have, respectively, energetic and entropic origins. The finding of such a cancellation between the two contributions to the osmotic pressure of the gel-solvent system is consistent with experimental observations that the swelling behavior of polyelectrolyte gels can be described by equations of state for neutral gels. Based on these results, we show and explain that a modified form of the Flory-Huggins model for nonionic polymer solutions, which accounts for neither electrostatic effects nor counterion excluded-volume effects, fits both experimental and simulated data for polyelectrolyte gels. The Flory-Huggins interaction parameters obtained from regression to the simulation data are characteristic of ideal polymer solutions, whereas the experimentally obtained interaction parameters, particularly that associated with the third virial coefficient, exhibit a significant departure from ideality, leading us to conclude that further enhancements to the simulation model, such as the inclusion of excess salt, the allowance for size asymmetric electrolytes, or the use of a distance-dependent solvent dielectricity model, may be required. Molecular simulations also reveal that the condensation of divalent counterions onto the polyelectrolyte network backbone occurs preferentially over that of monovalent counterions.

Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

PubMed Central

Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

2014-01-01

Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail. PMID:25532565

Design of chitosan and its water soluble derivatives-based drug carriers with polyelectrolyte complexes.

PubMed

Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

2014-12-19

Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brettmann, Blair; Pincus, Philip; Tirrell, Matthew

2017-01-13

We provide a theoretical model for the collapse of polyelectrolyte brushes in the presence of multivalent ions, focusing on the formation of lateral inhomogeneties in the collapsed state. Polyelectrolyte brushes are important in a variety of applications, including stabilizing colloidal particles and lubricating surfaces. Many uses rely on the extension of the densely grafted polymer chains from the surface in the extended brush morphology. In the presence Extended Brush of multivalent ions, brushes are significantly shorter than in monovalent ionic solutions, which greatly affects their properties. We base our theoretical analysis on an analogous collapse of polyelectrolyte brushes in amore » poor solvent, providing an energy balance representation for pinned micelles and cylindrical bundles. The equilibrium brush heights predicted for these structures are of a similar magnitude to those measured experimentally. The formation of lateral structures can open new avenues for stimuli-responsive applications that rely on nanoscale pattern formation on surfaces.« less

Nanohybrid conjugated polyelectrolytes: highly photostable and ultrabright nanoparticles.

PubMed

Darwish, Ghinwa H; Karam, Pierre

2015-10-07

We present a general and straightforward one-step approach to enhance the photophysical properties of conjugated polyelectrolytes. Upon complexation with an amphiphilic polymer (polyvinylpyrrolidone), an anionic conjugated polyelectrolyte (poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene]) was prepared into small nanoparticles with exceptional photostability and brightness. The polymer fluorescence intensity was enhanced by 23 -fold and could be easily tuned by changing the order of addition. Single molecule experiments revealed a complete suppression of blinking. In addition, after only losing 18% of the original intensity, a remarkable amount of photons were emitted per particle (∼10(9), on average). This number is many folds greater than popular organic fluorescent dyes. We believe that an intimate contact between the two polymers is shielding the conjugated polyelectrolyte from the destructive photooxidation. The prepared nanohybrid particles will prove instrumental in single particle based fluorescent assays and can serve as a probe for the current state-of-the-art bioimaging fluorescence techniques.

Influence of Hydrophobicity on Polyelectrolyte Complexation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadman, Kazi; Wang, Qifeng; Chen, Yaoyao

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP)more » with methyl, ethyl and propyl substituents– thereby increasing the hydrophobicity with increasing side chain length– and complexing them with a common anionic polyelectrolyte, poly(styrene sulfonate). The mechanical 1 ACS Paragon Plus Environment behavior of these complexes is compared to the more hydrophilic system of poly(styrene sulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling-modulus master curves that are quantified in this work. The rheological behavior of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.« less

Influence of Hydrophobicity on Polyelectrolyte Complexation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadman, Kazi; Wang, Qifeng; Chen, Yaoyao

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) withmore » methyl, ethyl, and propyl substituents—thereby increasing the hydrophobicity with increasing side chain length—and complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling–modulus master curves that are quantified in this work. Furthermore, the rheological behaviors of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.« less

Influence of Hydrophobicity on Polyelectrolyte Complexation

DOE PAGES

Sadman, Kazi; Wang, Qifeng; Chen, Yaoyao; ...

2017-11-16

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) withmore » methyl, ethyl, and propyl substituents—thereby increasing the hydrophobicity with increasing side chain length—and complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in response to salt stimuli. More hydrophobic complexes are found to be more resistant to doping by salt, yet the mechanical properties of the complex remain contingent on the overall swelling ratio of the complex itself, following near universal swelling–modulus master curves that are quantified in this work. Furthermore, the rheological behaviors of QVP complex coacervates are found to be approximately the same, only requiring higher salt concentrations to overcome strong hydrophobic interactions, demonstrating that hydrophobicity can be used as an important parameter for tuning the stability of polyelectrolyte complexes in general, while still preserving the ability to be processed “saloplastically”.« less

Influence of natural organic matter on equilibrium adsorption of neutral and charged pharmaceuticals onto activated carbon.

PubMed

de Ridder, D J; Verliefde, A R D; Heijman, S G J; Verberk, J Q J C; Rietveld, L C; van der Aa, L T J; Amy, G L; van Dijk, J C

2011-01-01

Natural organic matter (NOM) can influence pharmaceutical adsorption onto granular activated carbon (GAC) by direct adsorption competition and pore blocking. However, in the literature there is limited information on which of these mechanisms is more important and how this is related to NOM and pharmaceutical properties. Adsorption batch experiments were carried out in ultrapure, waste- and surface water and fresh and NOM preloaded GAC was used. Twenty-one pharmaceuticals were selected with varying hydrophobicity and with neutral, negative or positive charge. The influence of NOM competition and pore blocking could not be separated. However, while reduction in surface area was similar for both preloaded GACs, up to 50% lower pharmaceutical removal was observed on wastewater preloaded GAC. This was attributed to higher hydrophobicity of wastewater NOM, indicating that NOM competition may influence pharmaceutical removal more than pore blocking. Preloaded GAC was negatively charged, which influenced removal of charged pharmaceuticals significantly. At a GAC dose of 6.7 mg/L, negatively charged pharmaceuticals were removed for 0-58%, while removal of positively charged pharmaceuticals was between 32-98%. Charge effects were more pronounced in ultrapure water, as it contained no ions to shield the surface charge. Solutes with higher log D could compete better with NOM, resulting in higher removal.

Charge-Retraction Time-of-Flight Measurement for Organic Charge Transport Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, J.U.; Young, R.H.; Tang, C.W.

This describes an all-electrical technique, charge-retraction time-of-flight (CR-TOF), to measure charge carrier mobility through an organic layer. Carriers are injected and accumulated at a blocking interface, then retracted. The retraction current transient is nearly indistinguishable from a traditional time-of-flight photocurrent. The CR-TOF technique is validated by measurement of the hole mobility of two well-known compounds, 4,4',4"-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine and 4,4'-bis[N-1-napthyl)-N-phenylamino]biphenyl, utilizing 1,3,5-tris(N-phenylbenzimidazol-2-yl)-benzene as a hole-blocking layer.

An Examination of Protocols for The Collection of Munitions-Derived Explosives Residues on Snow-Covered Ice

DTIC Science & Technology

2005-04-01

with a single demolition block charge of C4 (DODIC M023) as the donor charge. An M739 point- detonating fuze (DODIC N340) was installed in each round...All rounds contained a supplementary TNT charge in the fuze well below the M739 fuze (see Appendix A). Figure 3 shows the setup common for all the...Charge, demolition block, Comp C4, M112 MA-97A003-007A 16 1390010809447 N340 Fuze, point detonating, M739 MA-84B007-013 7 Notes: Drawn from Fort