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Sample records for block polyelectrolyte solutions

  1. Molecular Dynamics Simulations of Polyelectrolyte Solutions

    Science.gov (United States)

    Dobrynin, Andrey

    2014-03-01

    Polyelectrolytes are polymers with ionizable groups. In polar solvents, these groups dissociate releasing counterions into solution and leaving uncompensated charges on the polymer backbone. Examples of polyelectrolytes include biopolymers such as DNA and RNA, and synthetic polymers such as poly(styrene sulfonate) and poly(acrylic acids). In this talk I will discuss recent molecular dynamics simulations of static and dynamic properties of polyelectrolyte solutions. These simulations show that in dilute and semidilute polyelectrolyte solutions the electrostatic induced chain persistence length scales with the solution ionic strength as I - 1 / 2. This dependence of the chain persistence length is due to counterion condensation on the polymer backbone. In dilute polyelectrolyte solutions the chain size decreases with increasing the salt concentration as R ~ I- 1 / 5. This is in agreement with the scaling of the chain persistence length on the solution ionic strength, lp ~ I- 1 / 2. In semidilute solution regime at low salt concentrations the chain size decreases with increasing polymer concentration, R ~ cp-1 / 4 . While at high salt concentrations one observes a weaker dependence of the chain size on the solution ionic strength, R ~ I- 1 / 8. Analysis of the simulation data throughout the studied salt and polymer concentration ranges shows that there exist general scaling relations between multiple quantities X (I) in salt solutions and corresponding quantities X (I0) in salt-free solutions, X (I) = X (I0) (I /I0) β . The exponent β = -1/2 for chain persistence length lp , β = 1/4 for solution correlation length, β = -1/5 and β = -1/8 for chain size R in dilute and semidilute solution regimes respectively. Furthermore, the analysis of the spectrum and of the relaxation times of Rouse modes confirms existence of the single length scale (correlation length) that controls both static and dynamic properties of semidilute polyelectrolyte solutions. These findings

  2. Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation.

    Science.gov (United States)

    Fan, Yin; Tang, Shengchang; Thomas, Edwin L; Olsen, Bradley D

    2014-11-25

    Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins.

  3. Molecular Thermodynamic Model for Polyelectrolyte Solutions with Added Salts

    Institute of Scientific and Technical Information of China (English)

    ZHANGBo; CAIJun; 等

    2002-01-01

    A molecular thermodynamic model of polyelectrolyte developed previously was extended to polyelectrolyte solutions with added salts.Thermodynamic properties,such as activity coefficients of polyelectrolytes or added salts and osmotic coefficients of solvent, of a number of aqueous mixtures of polyelectrolytes and salts are analyzed with the proposed model.Successful correlation is obtained in the range of moderate or higher polyion concentration.For the same sample,thermodynamic properties of polyelectrolytes with and without simple electrolytes can be predicted mutually using parameters from regression data.

  4. Salt Effect on Osmotic Pressure of Polyelectrolyte Solutions: Simulation Study

    Directory of Open Access Journals (Sweden)

    Jan-Michael Y. Carrillo

    2014-07-01

    Full Text Available Abstract: We present results of the hybrid Monte Carlo/molecular dynamics simulations of the osmotic pressure of salt solutions of polyelectrolytes. In our simulations, we used a coarse-grained representation of polyelectrolyte chains, counterions and salt ions. During simulation runs, we alternate Monte Carlo and molecular dynamics simulation steps. Monte Carlo steps were used to perform small ion exchange between simulation box containing salt ions (salt reservoir and simulation box with polyelectrolyte chains, counterions and salt ions (polyelectrolyte solution. This allowed us to model Donnan equilibrium and partitioning of salt and counterions across membrane impermeable to polyelectrolyte chains. Our simulations have shown that the main contribution to the system osmotic pressure is due to salt ions and osmotically active counterions. The fraction of the condensed (osmotically inactive counterions first increases with decreases in the solution ionic strength then it saturates. The reduced value of the system osmotic coefficient is a universal function of the ratio of the concentration of osmotically active counterions and salt concentration in salt reservoir. Simulation results are in a very good agreement with osmotic pressure measurements in sodium polystyrene sulfonate, DNA, polyacrylic acid, sodium polyanetholesulfonic acid, polyvinylbenzoic acid, and polydiallyldimethylammonium chloride solutions.

  5. Exploration of polyelectrolytes as draw solutes in forward osmosis processes

    KAUST Repository

    Ge, Qingchun

    2012-03-01

    The development of the forward osmosis (FO) process has been constrained by the slow development of appropriate draw solutions. Two significant concerns related to draw solutions are the draw solute leakage and intensiveenergy requirement in recycling draw solutes after the FO process. FO would be much attractive if there is no draw solute leakage and the recycle of draw solutes is easy and economic. In this study, polyelectrolytes of a series of polyacrylic acid sodium salts (PAA-Na), were explored as draw solutes in the FO process. The characteristics of high solubility in water and flexibility in structural configuration ensure the suitability of PAA-Na as draw solutes and their relative ease in recycle through pressure-driven membrane processes. The high water flux with insignificant salt leakage in the FO process and the high salt rejection in recycle processes reveal the superiority of PAA-Na to conventional ionic salts, such as NaCl, when comparing their FO performance via the same membranes. The repeatable performance of PAA-Na after recycle indicates the absence of any aggregation problems. The overall performance demonstrates that polyelectrolytes of PAA-Na series are promising as draw solutes, and the new concept of using polyelectrolytes as draw solutes in FO processes is applicable. © 2011 Elsevier Ltd.

  6. ANALYSIS OF VISCOSITY ABNORMALITIES OF POLYELECTROLYTES IN DILUTE SOLUTIONS

    Institute of Scientific and Technical Information of China (English)

    Jian-qiang Chen; Yu-fang Shao; Zhen Yang; Hu Yang; Rong-shi Cheng

    2011-01-01

    It was found that the interface effects in viscous capillary flow influenced the process of viscosity measurement greatly,and the abnormal viscosity behaviors of polyelectrolytes as well as neutral polymers in dilute solution region were ascribed to interface effect.According to this theory,we have reviewed the previous viscosity data of derivatives of poly-2-vinylpyridine reported by Maclay and Fuoss first.Then,the abnormal viscosity behaviors of a series of sodium polystyrene sulfonate samples with various molecular weights in dilute aqueous solutions were studied further.The solute adsorption behaviors and structural information of polymers have been discussed carefully.

  7. Aqueous dispersions of silver nanoparticles in polyelectrolyte solutions

    Indian Academy of Sciences (India)

    Dan Donescu; Raluca Somoghi; Marius Ghiurea; Raluca Ianchis; Cristian Petcu; Stefania Gavriliu; Magdalena Lungu; Claudia Groza; Carmen R Ionescu; Carmen Panzaru

    2013-03-01

    In this report, we present the versatile and effective technique, using environmental friendly reductant glucose, to prepare stable silver nanodispersions by reduction of Ag+ ions. Alternant copolymers of maleic anhydride with vinyl acetate and styrene sulphonate sodium acid salt polyelectrolytes were synthesized in aqueous solution and used as stabilizers. The formation of nano silver particles was confirmed by UV-Vis spectrophotometry and TEM measurements. Dynamic Light Scattering (DLS) measurements were needed to study how the reagents and their concentrations influence particle size. SEM images show the nanostructure of the hybrid films and indicate a strong interaction between the polyelectrolyte and the silver NPs. Moreover, the silver NPs could be stored for one year without observation of aggregates or sedimentation. The final solid products obtained after evaporating to dryness can be used to produce stable dispersions upon mixing with water. Few of the final products were found to exhibit a high antibacterial and antifungal activity.

  8. Porphyrin Diacid-Polyelectrolyte Assemblies: Effective Photocatalysts in Solution

    Directory of Open Access Journals (Sweden)

    Sabine Frühbeißer

    2016-05-01

    Full Text Available Developing effective and versatile photocatalytic systems is of great potential in solar energy conversion. Here we investigate the formation of supramolecular catalysts by electrostatic self-assembly in aqueous solution: Combining positively charged porphyrins with negatively charged polyelectrolytes leads to nanoscale assemblies where, next to electrostatic interactions, π–π interactions also play an important role. Porphyrin diacid-polyelectrolyte assemblies exhibit a substantially enhanced catalytic activity for the light-driven oxidation of iodide. Aggregates with the hexavalent cationic porphyrin diacids show up to 22 times higher catalytic activity than the corresponding aggregates under neutral conditions. The catalytic activity can be increased by increasing the valency of the porphyrin and by choice of the loading ratio. The structural investigation of the supramolecular catalysts took place via atomic force microscopy and small angle neutron scattering. Hence, a new facile concept for the design of efficient and tunable self-assembled photocatalysts is presented.

  9. Periodic nanoscale patterning of polyelectrolytes over square centimeter areas using block copolymer templates.

    Science.gov (United States)

    Oded, Meirav; Kelly, Stephen T; Gilles, Mary K; Müller, Axel H E; Shenhar, Roy

    2016-05-18

    Nano-patterned materials are beneficial for applications such as solar cells, opto-electronics, and sensing owing to their periodic structure and high interfacial area. Here, we present a non-lithographic approach for assembling polyelectrolytes into periodic nanoscale patterns over cm(2)-scale areas. Chemically modified block copolymer thin films featuring alternating charged and neutral domains are used as patterned substrates for electrostatic self-assembly. In-depth characterization of the deposition process using spectroscopy and microscopy techniques, including the state-of-the-art scanning transmission X-ray microscopy (STXM), reveals both the selective deposition of the polyelectrolyte on the charged copolymer domains as well as gradual changes in the film topography that arise from further penetration of the solvent molecules and possibly also the polyelectrolyte into these domains. Our results demonstrate the feasibility of creating nano-patterned polyelectrolyte layers, which opens up new opportunities for structured functional coating fabrication.

  10. Employment of Gibbs-Donnan-based concepts for interpretation of the properties of linear polyelectrolyte solutions

    Science.gov (United States)

    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.

  11. Adsorption of polyelectrolytes and charged block copolymers on oxides consequences for colloidal stability

    NARCIS (Netherlands)

    Hoogeveen, N.G.

    1996-01-01


    The aim of the study described in this thesis was to examine the adsorption properties of polyelectrolytes and charged block copolymers on oxides, and the effect of these polymers on the colloidal stability of oxidic dispersions. For this purpose the interaction of some well-characterised

  12. Adsorption of polyelectrolytes and charged block copolymers on oxides. Consequences for colloidal stability.

    NARCIS (Netherlands)

    Hoogeveen, N.G.

    1996-01-01

    The aim of the study described in this thesis was to examine the adsorption properties of polyelectrolytes and charged block copolymers on oxides, and the effect of these polymers on the colloidal stability of oxidic dispersions. For this purpose the interaction of some well-characterised polyelectr

  13. Solution properties of star polyelectrolytes having a moderate number of arms

    Science.gov (United States)

    Chremos, Alexandros; Douglas, Jack F.

    2017-07-01

    We investigate polyelectrolyte stars having a moderate number of arms by molecular dynamics simulations of a coarse-grained model over a range of polyelectrolyte concentrations, where both the counter-ions and solvent are treated explicitly. This class of polymeric materials is found to exhibit rather distinct static and dynamic properties from linear and highly branched star polyelectrolyte solutions emphasized in past studies. Moderately branched polymers are particle-like in many of their properties, while at the same time they exhibit large fluctuations in size and shape as in the case of linear chain polymers. Correspondingly, these fluctuations suppress crystallization at high polymer concentrations, leading apparently to an amorphous rather than crystalline solid state at high polyelectrolyte concentrations. We quantify the onset of this transition by measuring the polymer size and shape fluctuations of our model star polyelectrolytes and the static and dynamic structure factor of these solutions over a wide range of polyelectrolyte concentration. Our findings for star polyelectrolytes are similar to those of polymer-grafted nanoparticles having a moderate grafting density, which is natural given the soft and highly deformable nature of both of these "particles."

  14. Surface Tension and Lamellar Spacing in Polyelectrolyte Blends and Block Copolymers

    Science.gov (United States)

    Sing, Charles; Olvera de La Cruz, Monica

    2015-03-01

    Heterogeneous polymer systems such as block copolymers (BCPs) are governed primarily by a competition between the surface tension between different chemical species and the entropic stretching of the polymer chains. Charged BCPs represent a class of materials that is currently of great interest to the polymer community due to the promise of charged BCPs as nanostructured membranes for batteries and fuel cells. The inclusion of charge presents a powerful way to tune the structure of BCPs, and we develop our understanding of how to do so by investigating the interfacial properties (surface tension and microstructure size) of polyelectrolyte blends and block copolymers. We use a new method that combines the features of liquid state (LS) theory and self consistent field theory (SCFT) into a multiscale LS-SCFT theory that provides beyond-mean-field predictions of polyelectrolyte systems. We find that charge size, charge correlations, and the fraction of charged monomers plays a crucial role in determining surface tension, and we therefore demonstrate how BCP structure changes upon inclusion of charges. Finally, we will show that these predictions provide the ideal basis for comparison to experiment and subsequent refinement of LS-SCFT theory.

  15. Molecular Thermodynamic Model for Polyelectrolyte Solutions with Added Salts%含盐聚电解质溶液的分子热力学模型

    Institute of Scientific and Technical Information of China (English)

    张波; 蔡钧; 刘洪来; 胡英

    2002-01-01

    A molecular thermodynamic model of polyelectrolyte developed previously was extended to polyelectrolyte solutions with added salts. Thermodynamic properties, such as activity coefficients of polyelectrolytes or added salts and osmotic coefficients of solvent, of a number of aqueous mixtures of polyelectrolytes and salts are analyzed with the proposed model. Successful correlation is obtained in the range of moderate or higher polyion concentration. For the same sample, thermodynamic properties of polyelectrolytes with and without simple electrolytes can be predicted mutually using parameters from regression data.

  16. Condensation of semiflexible polyelectrolytes in mixed solutions of mono- and multivalent salts

    Science.gov (United States)

    Plunk, Amelia A.; Luijten, Erik

    2013-03-01

    The salt-dependent condensation of highly charged polyelectrolytes in aqueous solution is a topic of great biological and industrial importance that has been widely studied over the past decades. It is well established that interaction with multivalent counterions leads to the formation of bundle-like aggregates for rigid polyelectrolytes and to collapsed structures or disordered aggregates for flexible polyelectrolytes. Here, we investigate the behavior of semiflexible chain molecules, where the electrostatically induced aggregation is impeded by the intrinsic bending stiffness of the polymer. Moreover, we study the competition between monovalent and multivalent counterions in mixed solutions and establish the threshold salt concentration required for condensation. Our findings are relevant for a range of biomedical problems, including the fabrication of nanoparticles for gene delivery and the packaging of DNA by histones. This work is supported by the National Science Foundation.

  17. Preparation of conductive PDDA/(PEDOT:PSS) multilayer thin film: influence of polyelectrolyte solution composition.

    Science.gov (United States)

    Jurin, F E; Buron, C C; Martin, N; Filiâtre, C

    2014-10-01

    Self-assembled multilayer films made of PEDOT:PSS poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) and PDDA poly(diallyldimethylammonium chloride) were prepared using layer-by-layer method. In order to modify the growth regime of the multilayer, to fabricate an electrical conductive film and to control its thickness, the effects of pH, type of electrolyte, ionic strength and polyelectrolyte concentration were investigated. Optical reflectometry measurements show that the pH of the solutions has no effect on the film growth while the adsorbed amount increases more rapidly when BaCl2 is used instead of NaCl as electrolyte. An increase in the ionic strength (with NaCl) induces a change in the growth regime from a linear to an exponential one at low polyelectrolyte concentration. As UV-vis measurements indicate, no decomplexation of PEDOT was recorded after film preparation. With polyelectrolyte concentration below 1 g L(-1), no conductive films were obtained even if 50 bilayers were deposited. A conductive film was prepared with a polyelectrolyte concentration of 1 g L(-1) and the measured conductivity was 0.3 S m(-1). A slight increase in conductivity was recorded when BaCl2 was used probably due to a modification of the film structure. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Polyelectrolytes thermodynamics and rheology

    CERN Document Server

    P M, Visakh; Picó, Guillermo Alfredo

    2014-01-01

    This book discusses current development of theoretical models and experimental findings on the thermodynamics of polyelectrolytes. Particular emphasis is placed on the rheological description of polyelectrolyte solutions and hydrogels.

  19. Self-assembling Characteristics of Amphiphilic Star Block Copolymers with a Polyelectrolyte Shell

    Institute of Scientific and Technical Information of China (English)

    S.Strandman; A.Zarembo; V.Aseyev; S.J.Butcher; H.Tenhu

    2007-01-01

    1 Results Amphiphilic block copolymers are capable of forming supramolecular assemblies resembling those observed in nature,such as spherical micelles,worm micelles,and vesicles.Changing the solvent composition,ionic strength or pH of the polymer solution may induce the self-assembly of block copolymers or trigger the transition between the geometries of noncovalent assemblies.In the current work,we have synthesised starlike amphiphilic block copolymers having hydrophobic poly(methyl methacrylate),PMMA,...

  20. POLYMER COLLOIDS FORMED BY POLYELECTROLYTE COMPLEXATION OF VINYL POLYMERS AND POLYSACCHARIDES IN AQUEOUS SOLUTION

    Institute of Scientific and Technical Information of China (English)

    Hui-dan Liu; Takahiro Sato

    2013-01-01

    The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry,static and electrophoretic light scattering,and elementary analysis.Sodium salts of polyacrylate (PA) and heparin (Hep) were chosen as the polyanion,and hydrochloric salts of poly(vinyl amine) (PVA) and chitosan (Chts) as the polycation.Although these vinyl polymers and polysaccharides have remarkably different backbone chemical structures and linear charge densities,all the four combinations PA-PVA,PA-Chts,Hep-PVA,and Hep-Chts provide almost stoichiometric polyelectrolyte complexes which are slightly charged owing to the adsorption of the excess polyelectrolyte component onto the neutral complex.The charges stabilize the complex colloids in aqueous solution of a non-stoichiometric mixture,and the aggregation number of the complex colloids increases with approaching to the stoichiometric mixing ratio.The mixing ratio dependence of the aggregation number for the four complexes is explained by the model proposed in the previous study.

  1. Single chains of strong polyelectrolytes in aqueous solutions at extreme dilution: Conformation and counterion distribution

    Science.gov (United States)

    Xu, Guofeng; Luo, Shuangjiang; Yang, Qingbo; Yang, Jingfa; Zhao, Jiang

    2016-10-01

    The molecular conformation of two typical polyelectrolytes, sodium polystyrene sulfonate (NaPSS) and quarternized poly-4-vinylpyridine (QP4VP), was studied in aqueous solutions without salt addition at the single molecular level. By fluorescence correlation spectroscopy, the hydrodynamic radius (Rh) of NaPSS and QP4VP with the molecular weight ranging more than one order of magnitude was measured. The scaling analysis of Rh exhibits scaling exponent of 0.70 and 0.86 for NaPSS and QP4VP in solutions without added salts, respectively, showing the conformation is much more expanded than random coil. Numerical fittings using the model of diffusion of a rod molecule agree with the data well, indicating that the polyelectrolyte chains take the rod-like conformation under the condition without salt addition. Further investigations by determining the electric potential of single PSS- chains using the photon counting histogram technique demonstrate the enhanced counterion adsorption to the charged chain at higher molecular weight.

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

    Science.gov (United States)

    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

  3. Polyelectrolyte-like behaviour of poly(ethylene-oxide) solutions with added monovalent salt

    Science.gov (United States)

    Lal, Jyotsana; Hakem, Ilhem-Faiza

    2004-03-01

    Solvent effects on the conformation of poly(ethylene-oxide) (PEO) and complexation of PEO by monovalent cations, have been examined by using small-angle neutron scattering. In methanol and acetonitrile, a big change in interchain interaction, osmotic compressibility and local chain conformation have been observed upon addition of small amounts of potassium iodide. The amplitude of the total intensity decreases significantly and a peak at a certain value of the wavevector q* appears as signature of a polyelectrolyte-like behaviour. With further addition of salt, the ionic strength of the solution increases and potassium binding becomes less favorable: the binding constant decreases with the ionic strength and PEO behaves as a neutral polymer with excluded volume. No association between PEO and potassium iodide was observed in aqueous solutions. Reference: I.F. Hakem and J. Lal. Europhysics letters, 64 (2), 204, 2003

  4. Structure and dynamics of humic substances and model poly-electrolytes in solution; Structure et dynamique de substances humiques et polyelectrolytes modeles en solution

    Energy Technology Data Exchange (ETDEWEB)

    Roger, G.

    2010-09-15

    In the frame of a study about the feasibility of an underground storage of radioactive wastes, we focused on the role of degraded natural organic matter in the eventual transport of radionuclides in the environment. We are more interested by the determination of electro kinetic properties of these humic substances rather than the description of speciation reaction already widely discussed in the literature. We chose to determine the size and the charge of these humic substances thanks to an original method: high precision conductometry. This technique, associated to a suited transport theory, allows to describe the mobility of charged species in solution when taking into account the pairs interactions. We have participated in the development of this transport theory and we use it in order to determine the size and the charge of humic substances and a reference polyelectrolyte in different conditions of pH and ionic strength. All these experimental results obtained by conductometry were correlated with other experimental and theoretical methods: Atomic Force Microscopy, dynamic light scattering, laser zeta-metry and Monte-Carlo simulations. The obtained results confirm the generally admitted idea that humic substances are nano-metric entities having complexing properties towards cations and that can aggregate to form supra molecular structures. The effect of the ions present in the environment (sodium, calcium, magnesium) has been investigated. Finally the complexation of europium (which is considered as a good analogue of americium 241) has also been analysed by square wave voltammetry. (author)

  5. Metallosupramolecular coordination polyelectrolytes: potential building blocks for molecular-based devices.

    Science.gov (United States)

    Kurth, Dirk G

    2002-04-01

    Metal-ion-induced self-assembly of ditopic ligands, based on bisterpyridines, and transition metal ions result in formation of metallosupramolecular coordination polyelectrolytes (MEPE). The positive charge of MEPE can be utilized in several ways to process highly ordered architectures. Alternating adsorption of MEPE and oppositely charged polyelectrolytes on solid substrates results in multilayers. The sequential nature of this process allows combining MEPEs with other functional components. This process permits nanometer thickness control, is readily adapted for automated processing, and is applicable to two-dimensional substrates as well as to colloidal templates. The surface chemical properties of MEPE are readily controlled by complexing MEPE with negatively charged amphiphiles. The resulting polyelectrolyte-amphiphile complexes (PAC) are soluble in organic solvents and form liquid crystalline phases. The PAC also spreads at the air-water interface as Langmuir monolayer, which can be transferred onto solid substrates. The resulting Langmuir-Blodgett multilayers are highly ordered and anisotropic. Materials with transition metal ions possess many interesting properties, including spin transitions, magnetism, as well as photochemical assets that are relevant for the construction of functional devices and materials. The presented approach combines principles of supramolecular and colloidal chemistry as well as surface science, is highly modular in nature, and provides extensive control of structure and function from molecular to macroscopic levels.

  6. SANS from Salt-Free Aqueous Solutions of Hydrophilic and Highly Charged Star-Branched Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    François Boué

    2016-06-01

    Full Text Available Scattering functions of sodium sulfonated polystyrene (NaPSS star-branched polyelectrolytes with high sulfonation degrees were measured from their salt-free aqueous solutions, using the Small Angle Neutron Scattering (SANS technique. Whatever the concentration c, they display two maxima. The first, of abscissa q1*, is related to a position order between star cores and scales as q1* ∝ c1/3. The second, of abscissa q2*, is also observed in the scattering function of a semi-dilute solution of NaPSS linear polyelectrolytes. In the dilute regime (c < c*, non-overlapping stars, peak abscissa does not depend on concentration c and is just an intramolecular characteristic associated with the electrostatic repulsion between arms of the same star. In the semi-dilute regime, due to the star interpenetration, the scattering function – through the peak position, reflects repulsion between arms of the same star or of different stars. The c threshold between these distinct c-dependencies of q2* in the dilute and semi-dilute regimes is estimated as c*. Just as simple is the measurement of the geometrical radius R of the star obtained from the q1* value at c* through the relation 2R = 2π/q1*. By considering NaPSS stars of the same functionality with different degrees of polymerization per arm Na, we find R scaling linearly with Na, suggesting an elongated average conformation of the arms. This is in agreement with theoretical predictions and simulations. Meanwhile the value of q2* measured in the dilute regime does not allow any inhomogeneous counterion distribution inside the stars to be revealed.

  7. Counterion condensation of differently flexible polyelectrolytes in aqueous solutions in the dilute and semidilute regime.

    Science.gov (United States)

    Truzzolillo, D; Bordi, F; Cametti, C; Sennato, S

    2009-01-01

    The low-frequency limit of the electrical conductivity (dc conductivity) of differently flexible polyions in aqueous solutions has been measured over an extended polyion concentration range, covering both the dilute and semidilute (entangled and unentangled) regime, up to the concentrated regime. The data have been analyzed taking into account the different flexibility of the polymer chains according to the scaling theory of polyion solutions, in the case of flexible polyions, and according to the Manning model, in the case of rigid polyions. In both cases, the fraction f of free counterions, released into the aqueous phase from the ionizable polyion groups, has been evaluated and its dependence on the polyion concentration determined. Our results show that the counterion condensation follows at least three different regimes in dependence on the polyion concentration. The fraction f of free counterions remains constant only in the semidilute regime (a region that we have named the Manning regime), while there is a marked dependence on the polyion concentration both in the dilute and in the concentrated regime. These results are briefly discussed in the light of the scaling theory of polyelectrolyte aqueous solutions.

  8. Correlation between flexibility of chain-like polyelectrolyte and thermodynamic properties of its solution

    Directory of Open Access Journals (Sweden)

    T. Sajevic

    2011-09-01

    Full Text Available Structural and thermodynamic properties of the model solution containing charged oligomers and the equivalent number of counterions were studied by means of the canonical Monte Carlo simulation technique. The oligomers are represented as (flexible freely jointed chains or as a linear (rigid array of charged hard spheres. In accordance with the primitive model of electrolyte solutions, the counterions are modeled as charged hard spheres and the solvent as dielectric continuum. Significant differences in the pair distribution functions, obtained for the rigid (rod-like and flexible model are found but the differences in thermodynamic properties, such as, enthalpy of dilution and excess chemical potential, are less significant. The results are discussed in light of the experimental data an aqueous polyelectrolyte solutions. The simulations suggest that deviations from the fully extended (rod-like conformation yield slightly stronger binding of counterions. On the other hand, the flexibility of polyions, even when coupled with the ion-size effects, cannot be blamed for qualitative differences between the theoretical results and experimental data for enthalpy of dilution.

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

    Science.gov (United States)

    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.

  10. Osmosis and thermodynamics explained by solute blocking

    CERN Document Server

    Nelson, Peter Hugo

    2016-01-01

    A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic equilibrium occurs when the fraction of water molecules in solution matches the fraction of pure water molecules that have enough energy to overcome the pressure difference. Solute-blocking also provides a kinetic explanation for why Raoult's law and the other colligative properties depend on the mole fraction (but not the size) of the solute particles, resulting in a novel kinetic explanation for the entropy of mixing and chemical potential of ideal solutions. Some of its novel predictions have been confirmed, others can be tested experimentally or by simulation.

  11. Osmosis and thermodynamics explained by solute blocking.

    Science.gov (United States)

    Nelson, Peter Hugo

    2017-01-01

    A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic equilibrium occurs when the fraction of water molecules in solution matches the fraction of pure water molecules that have enough energy to overcome the pressure difference. Solute-blocking also provides a kinetic explanation for why Raoult's law and the other colligative properties depend on the mole fraction (but not the size) of the solute particles, resulting in a novel kinetic explanation for the entropy of mixing and chemical potential of ideal solutions. Some of its novel predictions have been confirmed; others can be tested experimentally or by simulation.

  12. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira

    2016-03-22

    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  13. Polyelectrolyte properties of biopolymers: conductivity and secondary structure of polyriboadenylic acid and its salts in solutions.

    Science.gov (United States)

    Kuznetsov, I A; Vorontsova, O V; Kozlov, A G

    1991-01-01

    Polyriboadenylates of alkali metals were obtained from (1) K(+)-poly(A) (salts 1) and (2) H(+)-poly(A) (salts II) by the ion-exchange method. The conductivity of these salts as well as of H(+)-poly(A) were studied. Salts I and II of the same counterion were shown to have significantly different conductivity coefficients (f) and polyion conductances (lambda 0p). the charge density parameter (xi) was 1.3 and 2.5, respectively, with lambda 0p equal to 44 and 83 ohm-1 cm2 mole-1 for poly(A)-I and poly(A)-II salts, respectively. This is credited to the difference in the conformations of corresponding polyions. The linear dependence of equivalent conductivity on the square root of polymer concentration (Kohlrausch coordinates), earlier obtained for DNA, is also satisfied for the studied polynucleotides. A comparison of the slopes of straight lines in Kohlrausch coordinates for poly(A), simple electrolytes, and for earlier studied polyribouridylic acid salts lends credence to the concepts, developed by a number of authors, that DNA can act as a "buffer" against the ion-ion interaction in concentrated electrolyte solutions. Using the approximation that the polyion conductance is independent of the counterion nature, parameter f (agreeing in this case with Eisenberg parameter phi) has been shown to decrease as the polynucleotide concentration is increased; the decrease is caused by the relaxation effect. The transference numbers of counterions, which have negative values in poly (A)-II solutions, grow with the increase in polymer concentration; the higher the xi, the more apparent is this increase. This is explained by the increase in the fraction of conductivity along the polyion chains ("surface" conductivity) with the growth of polyelectrolyte concentration.

  14. The model of a polyelectrolyte solution with explicit account of counterions within a self-consistent field theory

    Science.gov (United States)

    Budkov, Yu. A.; Nogovitsyn, E. A.; Kiselev, M. G.

    2013-04-01

    A theoretical approach to calculating the thermodynamic and structural functions of solutions of polyelectrolytes based on Gaussian equivalent representation for the calculation of functional integrals is proposed. It is noted that a new analytical result of this work is the direct assumption of counterions, along with an equation for the gyration radius of a polymer chain as a function of the concentrations of monomers and added low-molecular salt. An equation of state is obtained within the proposed model. Our theoretical results are used to describe the thermodynamic and structural properties of an aqueous solution of sodium polystyrene sulfonate with additions of NaCl.

  15. Concentration Dependent Structure of Block Copolymer Solutions

    Science.gov (United States)

    Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.

    2015-03-01

    Addition of solvent molecules into block copolymer can induce additional interactions between the solvent and both blocks, and therefore expands the range of accessible self-assembled morphologies. In particular, the distribution of solvent molecules plays a key role in determining the microstructure and its characteristic domain spacing. In this study, concentration dependent structures formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) solution in squalane are investigated using small-angle X-ray scattering. This reveals that squalane is essentially completely segregated into the PEP domains. In addition, the conformation of the PS block changes from stretched to nearly fully relaxed (i.e., Gaussian conformation) as amounts of squalane increases. NRF

  16. Characterization of a Model Polyelectrolyte Membrane Using a Semi-crystalline Block Copolymer

    Science.gov (United States)

    Beers, Keith; Wang, Xin; Balsara, Nitash

    2011-03-01

    The microstructured block copolymer sulfonated polystyrene-block-polyethylene is studied as model system for use as a proton exchange membrane in a fuel cell. Self-assembly of this system creates proton conducting hydrophilic channels in the form of sulfonated polystyrene domains, while the polyethylene domains create a hydrophobic matrix to provide mechanical stability. This system serves as a powerful model system since the effects of domain size, morphology and crystallinity on water uptake and proton conductivity can be investigated. Similar systems have shown the ability of small hydrophilic channels to prevent drying at high temperatures in humid air, but have focused on amorphous hydrophobic blocks. The morphology, water uptake, and proton conductivity of this semi-crystalline model system will be discussed.

  17. Chitosan-Based Zwitterionic Polyelectrolytes and Their N-Phosphobetainates: Facile Synthesis and Aqueous Solution Behaviors

    Institute of Scientific and Technical Information of China (English)

    Hongmei Kang; Yuanli Cai; Haijia Zhang; Junjie Deng; Pengsheng Liu

    2005-01-01

    @@ 1Introduction Chitosan has remarkable potential applications in pharmaceutical and cosmetic formulations[1], e.g. for drug delivery systems, tissue engineering, transplant and cell regeneration due to its excellent biocompatibility, biodegradability, mucoadhesion, etc. Its major drawback as considered for pharmaceutical and cosmetic formulations is its poor solubility due to strong hydrogen bonding and compact structures. Considerable efforts were focused on improving its solubility and enforcing its functionality[1]. As well-known that phosphorylcholine (PC), the structural component of cell membrane, is an amphiphile containing the zwitterionic quaternary ammonium and phosphonic acid moieties (phosphobetaine groups). There has been an intensive effort over the past decades to prepare and explore potential applications of the synthetic PC-polymers[2].In this paper, we describe a facile synthesis of chitosan derivatives containing zwitterionic secondary/tertiary amine and phosphonic acid groups and their further N-phosphobetainates. The polyelectrolyte effect and anti-polyelectrolyte effect of the chitosan-based zwitterionic polyelectrolytes were studied.

  18. Temperature-induced changes in polyelectrolyte films at the solid-liquid interface

    CERN Document Server

    Steitz, R; Tauer, K; Khrenov, Yu V; Klitzing, K V

    2002-01-01

    Polyelectrolyte multilayers (film thickness 30-60 nm) were built on top of silicon substrates by layer-by-layer deposition of oppositely charged polyelectrolytes from aqueous solutions. Three kinds of films were investigated: (A) films of a homo-polyelectrolyte and a diblock copolymer with a thermosensitive poly(N-isopropyl-acrylamide) block and (B) and (C) two reference systems built solely from homo-polyelectrolytes of opposite charges. Thermal behavior and subsequent structural changes of the functionalized films against D sub 2 O were investigated by neutron reflectometry. All films showed irreversible annealing effects upon heating. In addition, the thermosensitive films showed a decrease in thickness at elevated temperature (>30 C) while the reference samples, composed of thermo-insensitive polyelectrolytes only, did not. (orig.)

  19. Tuning Polyelectrolyte-Surfactant Interactions: Modification of Poly(ethylenimine) with Propylene Oxide and Blocks of Ethylene Oxide.

    Science.gov (United States)

    Penfold, J; Thomas, R K; Li, P; Batchelor, S N; Tucker, I M; Burley, A W

    2016-02-02

    Significantly enhanced adsorption at the air-water interface arises in polyelectrolyte/ionic surfactant mixtures, such as poly(ethylenimine)/sodium dodecyl sulfate (PEI/SDS), down to relatively low surfactant concentrations due to a strong surface interaction between the polyelectrolyte and surfactant. In the region of charge neutralization this can result in precipitation or coacervation and give rise to undesirable properties in many applications. Ethoxylation of the PEI can avoid precipitation, but can also considerably weaken the interaction. Localization of the ethoxylation can overcome these shortcomings. Further manipulation of the polyelectrolyte-surfactant interaction can be achieved by selective ethoxylation and propoxylation of the PEI amine groups. Neutron reflectivity and surface tension data are presented here which show how the polyelectrolyte-surfactant interaction can be manipulated by tuning the PEI structure. Using deuterium labeled surfactant and polymer the neutron reflectivity measurements provide details of the surface composition and structure of the adsorbed layer. The general pattern of behavior is that at low surfactant concentrations there is enhanced surfactant adsorption due to the strong surface interaction; whereas around the region of the SDS critical micellar concentration, cmc, the surface is partially depleted of surfactant in favor bulk aggregate structures. The results presented here show how these characteristic features of the adsorption are affected by the degree of ethoxylation and propoxylation. Increasing the degree of propoxylation enhances the surfactant adsorption, whereas varying the degree of ethoxylation has a less pronounced effect. In the region of surfactant surface depletion increasing both the degree of ethoxylation and propoxylation result in an increased surface depletion.

  20. Ophthalmic regional blocks: management, challenges, and solutions

    Directory of Open Access Journals (Sweden)

    Palte HD

    2015-08-01

    Full Text Available Howard D Palte Department of Anesthesiology, Perioperative Medicine and Pain Management, Miller School of Medicine, University of Miami, Miami, FL, USA Abstract: In the past decade ophthalmic anesthesia has witnessed a major transformation. The sun has set on the landscape of ophthalmic procedures performed under general anesthesia at in-hospital settings. In its place a new dawn has ushered in the panorama of eye surgeries conducted under regional and topical anesthesia at specialty eye care centers. The impact of the burgeoning geriatric population is that an increasing number of elderly patients will present for eye surgery. In order to accommodate increased patient volumes and simultaneously satisfy administrative initiatives directed at economic frugality, administrators will seek assistance from anesthesia providers in adopting measures that enhance operating room efficiency. The performance of eye blocks in a holding suite meets many of these objectives. Unfortunately, most practicing anesthesiologists resist performing ophthalmic regional blocks because they lack formal training. In future, anesthesiologists will need to block eyes and manage common medical conditions because economic pressures will eliminate routine preoperative testing. This review addresses a variety of topical issues in ophthalmic anesthesia with special emphasis on cannula and needle-based blocks and the new-generation antithrombotic agents. In a constantly evolving arena, the sub-Tenon’s block has gained popularity while the deep angulated intraconal (retrobulbar block has been largely superseded by the shallower extraconal (peribulbar approach. Improvements in surgical technique have also impacted anesthetic practice. For example, phacoemulsification techniques facilitate the conduct of cataract surgery under topical anesthesia, and suture-free vitrectomy ports may cause venous air embolism during air/fluid exchange. Hyaluronidase is a useful adjuvant because it

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

    Science.gov (United States)

    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.

  2. Biological and Biomimetic Comb Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Aristeidis Papagiannopoulos

    2010-05-01

    Full Text Available Some new phenomena involved in the physical properties of comb polyelectrolyte solutions are reviewed. Special emphasis is given to synthetic biomimetic materials, and the structures formed by these molecules are compared with those of naturally occurring glycoprotein and proteoglycan solutions. Developments in the determination of the structure and dynamics (viscoelasticity of comb polymers in solution are also covered. Specifically the appearance of multi-globular structures, helical instabilities, liquid crystalline phases, and the self-assembly of the materials to produce hierarchical comb morphologies is examined. Comb polyelectrolytes are surface active and a short review is made of some recent experiments in this area that relate to their morphology when suspended in solution. We hope to emphasize the wide variety of phenomena demonstrated by the vast range of naturally occurring comb polyelectrolytes and the challenges presented to synthetic chemists designing biomimetic materials.

  3. Hydrophobically modified polyelectrolytes I. Dilute solution properties of fluorocarbon-containingpoly(acrylic acid)

    Institute of Scientific and Technical Information of China (English)

    ZHOU, Hui(周晖); SONG, Guo-Qiang(宋国强); ZHANG, Yun-Xiang(章云祥); DIEING, Reinhold; MA, Lian; HAEUSSLING, Lukas

    2000-01-01

    Dilute solution viscosity of fluorocarbon-containing hydrophobically modified poly(acrylic acid) was measured in aqueous solutions of various NaCl concentrations. The intrinsic viscosity ([η]) and Huggins coefficient (kH) were evaluated using Huggins equations. It is found that, at low NaCl concentration, the modified polymers exhibit values of intrinsic viscosity ( [η] ) and Huggins coefficient (kH) similar to those of unmodified polymers. For both of the modified and unmodified polymers, the intrinsic viscosity decreases with increase of NaCl concentration, while the Huggins coefficient increases upon addition of NaCl. But the variation of [η] and kH is more significant for the modified polymers, which reflects the enhanced intra- and intermolecular hydrophobic association at higher NaCl concentration.

  4. Precipitation polymerization of hydrophobically modified polyelectrolyte poly(AA-co-ODA) in supercritical carbon dioxide and solution rheology properties

    Science.gov (United States)

    Zhang, Huaiping; Li, Wei; Cao, Qing; Chen, Mingcai

    2014-05-01

    Hydrophobically modified (HM) polyelectrolytes were prepared by using precipitation polymerization of acrylic acid (AA) and octadecyl acrylate (ODA) in various molar ratios in supercritical carbon dioxide. The product was obtained in the form of a white powder and the micrographs show aggregates of primary particles properties.

  5. Guided wave sensing of polyelectrolyte multilayers

    DEFF Research Database (Denmark)

    Horvath, R.; Pedersen, H.C.; Cuisinier, F.J.G.

    2006-01-01

    A planar optical waveguide configuration is proposed to monitor the buildup of thick polyelectrolyte multilayers on the surface of the waveguide in aqueous solutions. Instead of detecting the layer by the electromagnetic evanescent field the polyelectrolyte layer acts as an additional waveguiding...... film that is sensed by guided waves instead of evanescent waves. This leads to a considerably improved sensitivity and dynamic range....

  6. Self-assembly in casting solutions of block copolymer membranes

    KAUST Repository

    Marques, Debora S.

    2013-01-01

    Membranes with exceptional pore regularity and high porosity were obtained from block copolymer solutions. We demonstrate by small-angle X-ray scattering that the order which gives rise to the pore morphology is already incipient in the casting solution. Hexagonal order was confirmed in PS-b-P4VP 175k-b-65k solutions in DMF/THF/dioxane with concentrations as high as 24 wt%, while lamellar structures were obtained in more concentrated solutions in DMF or DMF/dioxane. The change in order has been understood with the support of dissipative particle dynamic modeling. © 2013 The Royal Society of Chemistry.

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

    Science.gov (United States)

    Plazzotta, Beatrice; Diget, Jakob Stensgaard; Zhu, Kaizheng; Nyström, Bo; Pedersen, Jan Skov

    2016-10-01

    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.

  8. Ionizing radiation in the polyelectrolytes technology

    Science.gov (United States)

    Martin, D.; Dragusin, M.; Radoiu, M.; Moraru, R.; Oproiu, C.; Toma, M.; Ferdes, O.; Jianu, A.; Bestea, V.; Manea, A.

    1999-01-01

    Gamma ray and accelerated electron beam application in the chemistry of polyelectrolytes is presented. The polyelectrolytes preparation is based on radiation induced polymerization of aqueous solutions containing an appropriate mixture of monomers such as acrylamide, acrylic acid, vinyl acetate, diallyldimethylammonium-chloride and certain initiators, complexing agents and chain transfer agents. The effects of absorbed dose, rate of absorbed dose and chemical composition of aqueous solution on the polymerization process are discussed. The results obtained by testing these polyelectrolytes with waste water from food industry are also given.

  9. Excimer formation and singlet-singlet energy transfer of organoluminophores in the premicellar and micellar-polyelectrolytes solutions

    Science.gov (United States)

    Bisenbaev, Adel K.; Levshin, L. V.; Saletsky, A. M.

    1991-05-01

    Recently the investigation of photoprocesses in organized synthetical structures (ionic micelles, vesicles, linear polyelectrolytes, polymer gels etc.), intermolecular interactions of which are formed by hydrophobic and electric forces, have been of great interest.12 These systems are of particular interest due to the possibility of using luminescent data, which reflected the peculiarities of photoprocesses in organized assemblies. This can be used to establishing the mechanism of photobiological processes. Due to the very complex nature of biostructures our approximation can be considered phenomenological, however it gives the possibility of revealing the energy dissipation path in biosystems. Such model approach is based on a principal resemblance between a living matter and synthetical polymolecular structures with a certain degree of organization. This resemblance is displayed in theoretical models of synthetic polymers,3 which are the foundation of modern ideas on biomolecule conformation. Organized synthetical structures like ionic micelles, polymer gel, bilayer and strong polyelectrolytes could be made to represent biosystems like cell, protoplasm, membrane and NADH, respectively. In this paper we report some new results on the complex formation of dyes and detergents in premicellar region and singlet-singlet energy transfer from pyrene (Py) excimer to dye monomers in ionic micellar-polyion-water system.

  10. Stability of ordered phases in block copolymer melts and solutions

    Indian Academy of Sciences (India)

    Kell Mortensen

    2008-11-01

    Block copolymer melts and solutions assemble into nanosized objects that order into a variety of phases, depending on molecular parameters and mutual interactions. Beyond the classical phases of lamella ordered sheets, hexagonally ordered cylinders and cubic ordered spheres, the complex bicontinuous gyroid phase and the modulated lamellar phase are observed near the phase boundaries. The stability of these phases has been discussed on the basis of theoretical calculations. Here, we will discuss new experimental results showing that the given ordered phase depends critically on both molecular purity and mechanical treatment of the sample. While a variety of block copolymer micellar systems have been shown to undergo the liquid-to-bcc-to-fcc phase sequence upon varying micellar parameters (or temperature), we find for a purified system a different sequence, namely liquid-to-fcc-to-bcc [1]. The latter sequence is by the way the one predicted for pure block copolymer melts. External fields like shear or stress may also affect the ordered phase. Applying well-controlled large-amplitude oscillatory shear can be used to effectively control the texture of soft materials in the ordered states. As an example, we present results on a body-centred-cubic phase of a block copolymer system, showing how a given texture can be controlled with the application of specific shear rate and shear amplitude [2,3]. Shear may however also affect the thermodynamic ground state, causing shear-induced ordering and disordering (melting), and shear-induced order–order transitions. We will present data showing that the gyroid state of diblock copolymer melts is unstable when exposed to large amplitude/frequency shear, transforming into the hexagonal cylinder phase [4]. The transformation is completely reversible. With the rather slow kinetics in the transformation of copolymer systems, it is possible in detail to follow the complex transformation process, where we find transient ordered

  11. Complex Formation Between Polyelectrolytes and Ionic Surfactants

    OpenAIRE

    1998-01-01

    The interaction between polyelectrolyte and ionic surfactant is of great importance in different areas of chemistry and biology. In this paper we present a theory of polyelectrolyte ionic-surfactant solutions. The new theory successfully explains the cooperative transition observed experimentally, in which the condensed counterions are replaced by ionic-surfactants. The transition is found to occur at surfactant densities much lower than those for a similar transition in non-ionic polymer-sur...

  12. Charge-regularization effects on polyelectrolytes

    Science.gov (United States)

    Muthukumar, Murugappan

    2012-02-01

    When electrically charged macromolecules are dispersed in polar solvents, their effective net charge is generally different from their chemical charges, due to competition between counterion adsorption and the translational entropy of dissociated counterions. The effective charge changes significantly as the experimental conditions change such as variations in solvent quality, temperature, and the concentration of added small electrolytes. This charge-regularization effect leads to major difficulties in interpreting experimental data on polyelectrolyte solutions and challenges in understanding the various polyelectrolyte phenomena. Even the most fundamental issue of experimental determination of molar mass of charged macromolecules by light scattering method has been difficult so far due to this feature. We will present a theory of charge-regularization of flexible polyelectrolytes in solutions and discuss the consequences of charge-regularization on (a) experimental determination of molar mass of polyelectrolytes using scattering techniques, (b) coil-globule transition, (c) macrophase separation in polyelectrolyte solutions, (c) phase behavior in coacervate formation, and (d) volume phase transitions in polyelectrolyte gels.

  13. Stabilization and controlled association of superparamagnetic nanoparticles using block copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Frka-Petesic, Bruno [UPMC Univ Paris 6, Lab. des Liquides Ioniques et Interfaces Chargees (LI2C), CNRS-ESPCI UMR 7612 case 51, 4 place Jussieu, F-75252 Paris Cedex 05 (France); Fresnais, Jerome; Berret, Jean-Francois [Laboratoire Matiere et Systemes Complexes (MSC), UMR 7057 CNRS and Universite Paris Diderot, Batiment Condorcet 10 rue Alice Domon et Leonie Duquet, F-75205 Paris Codex 13 (France); Dupuis, Vincent [UPMC Univ Paris 6, Lab. des Liquides Ioniques et Interfaces Chargees (LI2C), CNRS-ESPCI UMR 7612 case 51, 4 place Jussieu, F-75252 Paris Cedex 05 (France); Perzynski, Regine [UPMC Univ Paris 6, Lab. des Liquides Ioniques et Interfaces Chargees (LI2C), CNRS-ESPCI UMR 7612 case 51, 4 place Jussieu, F-75252 Paris Cedex 05 (France)], E-mail: regine.perzynski@upmc.fr; Sandre, Olivier [UPMC Univ Paris 6, Lab. des Liquides Ioniques et Interfaces Chargees (LI2C), CNRS-ESPCI UMR 7612 case 51, 4 place Jussieu, F-75252 Paris Cedex 05 (France)

    2009-04-15

    Mixing in aqueous solutions polyelectrolyte-neutral block copolymers with oppositely charged species, spontaneously forms stable core-shell complexes, which are electrostatically driven. We report here on the structural and orientational properties of such mixed magnetic nanoclusters made of magnetic iron oxide nanoparticles (MNPs) and polyelectrolyte-neutral block copolymers. Small angle neutron scattering and transmission electron microscopy experiments allows to probe the inner-core nanoparticle organization, leading to an average interparticle distance and confirming the hierarchical internal structure of the clusters. Thanks to the MNP optical anisotropy, we also probe the under-magnetic field orientational properties of the core-shell clusters and their dynamical rotational relaxation.

  14. Effect of dipping solution pH values on electrostatic layer-by-layer self-assembly of side-chain azo polyelectrolyte

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The effect of pH value on the electrostatic layer-by-layer self-assembly and the photo-responsive behavior of Poly{2-[4-(4-ethoxyphenylazo)phenoxy]ethyl acrylate-co-acrylic acid} (PEAPE) was studied.Results show that in the studied pH value range,the lower the pH value is,the higher is the UV-vis absorbance and the larger is the thickness of the multilayer films.FTIR studies indicate that the azo polyelectrolyte exhibits a different ionization degree in solutions with different pH values.The higher absorbance and the larger thickness of the layer-by-layer films can be attributed to the low ionization degree and the shrinkage conformation of PEAPE in the solution with low pH values.FTIR analysis also confirms that the driving force for layer-by-layer self-assembly of PEAPE and PDAC is the electrostatic interaction.

  15. Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

    CERN Document Server

    Voisin, D

    2002-01-01

    Oppositely charged surfactant and polyelectrolyte are present in hair shampoos and conditioners, together with particles (e.g. anti-dandruff agents for scalp) and droplets (e.g. silicone oil for the hair). These are normally formulated at high surfactant concentrations, beyond the flocculation region for the polyelectrolyte concentration used. However, on dilution with water, during application, flocs are formed which carry the particles and droplets to the scalp and hair. The addition of an anionic surfactant to an aqueous solution of cationic polyelectrolyte, at a given concentration, can lead to the formation of polyelectrolyte-surfactant 'particles', in which the surfactant 'binds' to the polyelectrolyte. This occurs from the critical association concentration (CAC), up to the surfactant concentration corresponding to maximum binding. Within this range of surfactant concentrations, the surfactant bound to the polyelectrolyte is thought to associate to form what might be termed 'internal micelles'. Each po...

  16. Charged colloids, polyelectrolytes and biomolecules viewed as strongly coupled Coulomb systems

    CERN Document Server

    Löwen, H; Likos, C N; Blaak, R; Dzubiella, J; Jusufi, A; Hoffmann, N; Harreis, H M

    2003-01-01

    A brief review is given on recent studies of charged soft matter solutions, as modelled by the 'primitive' approach of strongly coupled Coulomb systems, where the solvent just enters as a dielectric background. These include charged colloids, biological macromolecules such as proteins and DNA, polyelectrolytes and polyelectrolyte stars. Also some original results are presented on colloid-polyelectrolyte complex formation near walls and on the anomalous fluid structure of polyelectrolyte stars as a function of increasing concentration.

  17. Hydrophobically modified polyelectrolytes : synthesis, properties and interactions with surfactants

    NARCIS (Netherlands)

    Nieuwkerk, A.C.

    1998-01-01

    Hydrophobically modified polyelectrolytes can form micelle-like aggregates, so-called microdomains, in aqueous solution. The hydrophobic side chains constitute the apolar inner part of these microdomains and the hydrophilic groups on the polyelectrolyte backbone are at the surface of the

  18. Saloplastics: processing compact polyelectrolyte complexes.

    Science.gov (United States)

    Schaaf, Pierre; Schlenoff, Joseph B

    2015-04-17

    Polyelectrolyte complexes (PECs) are prepared by mixing solutions of oppositely charged polyelectrolytes. These diffuse, amorphous precipitates may be compacted into dense materials, CoPECs, by ultracentrifugation (ucPECs) or extrusion (exPECs). The presence of salt water is essential in plasticizing PECs to allow them to be reformed and fused. When hydrated, CoPECs are versatile, rugged, biocompatible, elastic materials with applications including bioinspired materials, supports for enzymes and (nano)composites. In this review, various methods for making CoPECs are described, as well as fundamental responses of CoPEC mechanical properties to salt concentration. Possible applications as synthetic cartilage, enzymatically active biocomposites, self-healing materials, and magnetic nanocomposites are presented.

  19. Electrostatics of Rigid Polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Wong, G.C.L.

    2009-06-04

    The organization of rigid biological polyelectrolytes by multivalent ions and macroions are important for many fundamental problems in biology and biomedicine, such as cytoskeletal regulation and antimicrobial sequestration in cystic fibrosis. These polyelectrolytes have been used as model systems for understanding electrostatics in complex fluids. Here, we review some recent results in theory, simulations, and experiments.

  20. Polyelectrolyte properties of proteoglycan monomers

    Science.gov (United States)

    Li, Xiao; Reed, Wayne F.

    1991-03-01

    Light scattering measurements were made on proteoglycan monomers (PGM) over a wide range of ionic strengths Cs, and proteoglycan concentrations [PG]. At low Cs there were clear peaks in the angular scattering intensity curve I(q), which moved towards higher scattering wave numbers q, as [PG]1/3. This differs from the square root dependence of scattering peaks found by neutron scattering from more concentrated polyelectrolyte solutions. The peaks remained roughly fixed as Cs increased, but diminished in height, and superposed I(q) curves yielded a sort of isosbestic point. Under certain assumptions the static structure factor S(q) could be extracted from the measured I(q), and was found to retain a peak. A simple hypothesis concerning coexisting disordered and liquidlike correlated states is presented, which qualitatively accounts for the most salient features of the peaks. There was evidence of a double component scattering autocorrelation decay at low Cs, which, when resolved into two apparent diffusion coefficients, gave the appearance of simultaneous ``ordinary'' and ``extraordinary'' phases. The extraordinary phase was ``removable,'' however, by filtering. At higher Cs the proteoglycans appear to behave as random nonfree draining polyelectrolyte coils, with a near constant ratio of 0.67 between hydrodynamic radius and radius of gyration. The apparent persistence length varied as roughly the -0.50 power of ionic strength, similar to various linear synthetic and biological polyelectrolytes. Electrostatic excluded volume theory accounted well for the dependence of A2 on Cs.

  1. Polyelectrolyte multilayers: An odyssey through interdisciplinary science

    Science.gov (United States)

    Jaber, Jad A.

    This dissertation provides an overview of a self assembled multilayer technique based on the alternating deposition of oppositely charged polyelectrolytes onto charged solid supports. The basic principles and methodologies governing this technique are laid down, and new strategies are built upon the latter, in an effort to develop innovative technologies that would be beneficial for making new products or improving the quality of existing ones. Fundamental studies to characterize the water content, efficiency of ion-pairing, differential strength of electrostatic interactions, topology, and viscoelastic properties of polyelectrolyte multilayers, PEMUs, are illustrated and conducted. In addition, polyelectrolyte multilayers that are stimulus responsive, or support active and controlled bio-motor protein interactions are described. Attenuated total reflectance Fourier transform infrared, (ATR), spectroscopy was used to compare the extent of swelling and doping within PAH/PSS and PDADMA/PSS polyelectrolyte multilayers. Unlike PDADMA/PSS, whose water content depended on the solution ionic strength, PAH/PSS was resistant to swelling by salt. It was stable up to 4.0 M sodium chloride, with 6 water molecules per ion-pair. Using the infrared active perchlorate sodium salt, the amount of residual persistent extrinsic sites in both PDADMA/PSS and PAH/PSS was determined to be 3% and 6%, respectively. The free energy of association between the polymer segments, in the presence of sodium perchlorate, was in the order of 4.5 kJ mol-1 and -9.5 kJ mol-1 for PDADMA/PSS and PAH/PSS correspondingly. Thus, indicating the relatively strong electrostatic association between the polymer segments in a PAH/PSS relative to PDADMA/PSS multilayer. Adjusting the pH of the solution in contact with the PAH/PSS multilayer to 11.5 resulted in a first order discontinuous dissociation of the Pol+Pol- bonds. Techniques used to study the mechanical properties of single muscle fiber were adapted to

  2. Investigating self-assembly and metal nanoclusters in aqueous di-block copolymers solutions

    CERN Document Server

    Lo Celso, F; Triolo, R; Triolo, A; Strunz, P; Bronstein, L; Zwanziger, J; Lin, J S

    2002-01-01

    Self-assembling properties of di-block copolymers/ surfactant hybrids in aqueous solution can be exploited to obtain metal nanoparticles stable dispersion. Results will be presented here for polystyrene-block-poly(ethylene oxide) solutions. A SANS structural investigation has been performed over different molecular weights of both hydrophilic and hydrophobic block, by varying temperature and concentration of the copolymer. A SAXS characterization of micellar systems containing Pt nanoparticles is reported. (orig.)

  3. Synthesis and solution self-assembly of side-chain cobaltocenium-containing block copolymers.

    Science.gov (United States)

    Ren, Lixia; Hardy, Christopher G; Tang, Chuanbing

    2010-07-07

    The synthesis of side-chain cobaltocenium-containing block copolymers and their self-assembly in solution was studied. Highly pure monocarboxycobaltocenium was prepared and subsequently attached to side chains of poly(tert-butyl acrylate)-block-poly(2-hydroxyethyl acrylate), yielding poly(tert-butyl acrylate)-block-poly(2-acryloyloxyethyl cobaltoceniumcarboxylate). The cobaltocenium block copolymers exhibited vesicle morphology in the mixture of acetone and water, while micelles of nanotubes were formed in the mixture of acetone and chloroform.

  4. Characterization for Soil Fixation by Polyelectrolyte Complex

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yong Suk; Kwon, Sang Woon; Yang, Heeman; Lee, Kune Woo; Seo, Bumkyoung; Moon, Jei Kwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-05-15

    According to report, the radioactivity bulk (approx. 95%) is localized within topsoil. Therefore soil surface on topsoil should be fixed to prevent the spreading of the contaminated soils with Cs-137 by wind and water erosion. Many methods have been developing for soil fixation to remove radioactive contaminants in soil and prevent to diffuse radioactive materials. Various materials have been also used as fixatives such as clays, molecular sieves, polymer, and petroleum based products. One of the methods is a soil fixation or solidification using polyelectrolyte. Polyelectrolytes have many ionic groups and make into the polyelectrolyte complex (PEC) due to electrostatic interaction of polyanion and polycation in an aqueous solution. It can be avoids using the chemical cross-linking agents, and reducing the possible toxicity and other undesirable effects of the reagents. PEC can fix soil particles by flocculation and formation of crust between soil. The method can also prevent a spread of radioactive material by floating on a soil surface. Recently, PEC used for the solidification of soil near the Fukushima nuclear power plant in Japan. The decontamination efficiency of the surface soils reached 90%, and dust release was effectively suppressed during the removal of surface soils. In this study, it was investigated the fixation of the soil by PEC to avoid the spread of the contamination in addition to the separation of soil and PEC. The physicochemical properties of polyelectrolyte complex solution and the stability of fixed soil by PEC were investigated. The mode of the addition is important to prepare the polyelectrolytes complex without PAA agglomerate. The concentration of salt in the polyelectrolyte complex solution is a very important parameter for the soil fixation.

  5. PERMEATION OF POLYELECTROLYTES AND OTHER SOLUTES INTO THE PORE SPACES OF WATER-SWOLLEN CELLULOSE: A REVIEW

    OpenAIRE

    Ning Wu; Martin A. Hubbe; Rojas, Orlando J.; Sunkyu Park

    2009-01-01

    The rate and extent of transport of macromolecules and other solutes into cellulosic materials and fibers have important applications in such fields as papermaking, textiles, medicine, and chromatography. This review considers how diffusion and flow affect permeation into wood, paper, and other lignocellulosic materials. Because pore sizes within such materials can range from nanometers to millimeters, a broad perspective will be used, also considering some publications related to other por...

  6. PERMEATION OF POLYELECTROLYTES AND OTHER SOLUTES INTO THE PORE SPACES OF WATER-SWOLLEN CELLULOSE: A REVIEW

    Directory of Open Access Journals (Sweden)

    Ning Wu

    2009-08-01

    Full Text Available The rate and extent of transport of macromolecules and other solutes into cellulosic materials and fibers have important applications in such fields as papermaking, textiles, medicine, and chromatography. This review considers how diffusion and flow affect permeation into wood, paper, and other lignocellulosic materials. Because pore sizes within such materials can range from nanometers to millimeters, a broad perspective will be used, also considering some publications related to other porous materials. Factors that limit the rate or extent of polymer or other solute transport into pores can involve thermodynamics (affecting the driving motivation for permeation, kinetics (if there is insufficient time for the system to come to equilibrium, and physical barriers. Molecular flow is also affected by the attributes of the solute, such as molecular mass and charge, as well as those of the substrate, such as the pore size, interconnectedness, restricted areas, and surface characteristics. Published articles have helped to clarify which of these factors may have a controlling influence on molecular transport in different situations.

  7. Immunoblotting with monoclonal antibodies: importance of the blocking solution.

    Science.gov (United States)

    Hauri, H P; Bucher, K

    1986-12-01

    Four commonly used blocking agents, i.e., fetal calf serum, mammalian gelatin-Nonidet-P40, fish gelatin-Nonidet-P40, and defatted powdered milk were compared with respect to their efficiency to block the nonspecific background and to promote maximal immunoreactivity of monoclonal antibodies against human intestinal sucrase-isomaltase during immunoblotting. Two of five monoclonal antibodies were found to react with the electroblotted enzyme. However, one of the reacting antibodies gave optimal results with fish gelatin-Nonidet-P40 and the other with defatted powdered milk, while fetal calf serum lead to unacceptably high backgrounds. The results suggest that some of the difficulties encountered with monoclonal antibodies in immunoblotting may be due to inappropriate blocking conditions.

  8. Self-assembled Structures of a Multifunctional, Structured Block Copolymer in Solution; A SANS Study

    Science.gov (United States)

    Etampawala, Thusitha; Senanayake, Manjula; Osti, Naresh; He, Lilin; Heller, William; Perahia, Dvora

    2014-03-01

    The self-assembly of multi block copolymer in solutions is controlled by a delicate balance between inherent phase segregation due to incompatibility of the blocks and the interactions of the individual blocks with the solvent. We investigated the association of ABCBA penta-block copolymers, in solution using Small angle neutron scattering (SANS). The ABCBA penta-block comprises of centered randomly sulfonated polystyrene block to which rubbery polyisoprene is connected, terminated by blocks of polystyrene decorated with tertiary butyl group, kindly provided by Kraton LLC. The SANS studies have shown that the penta-block forms ellipsoidal core-shell structures with the sulfonated polystyrene in the core and Gaussian decaying chains of swollen polyisoprene and tertiary butyl polystyrene in the corona. The size of the micelle, the thickness of the corona and the aggregation number increased with increasing the solution concentration and temperature, while the solvent fraction in the core decreased. The dilute solutions promptly responded to thermal fluctuations. However, the temperature effects disappeared with increasing the solution concentration.

  9. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

    Science.gov (United States)

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

    2017-03-01

    Calcium carbonate (CaCO3) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO4·2H2O and CaSO4 transformed into calcite, a polymorph of CaCO3, while maintaining their macroscopic structure when immersed in 1mol/L Na2CO3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO4·2H2O and CaSO4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO4·2H2O and CaSO4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors.

  10. Magicians fix your mind: How unlikely solutions block obvious ones.

    Science.gov (United States)

    Thomas, Cyril; Didierjean, André

    2016-09-01

    In everyday life, several factors limit the human capacity to think differently. The present study shows that implanting an unlikely and unfamiliar idea in the mind can prevent participants from finding a more obvious one. To demonstrate this, we used a technique often adopted by magicians to misrepresent the method of a trick: the false solution. Our results reveal that a single exposure to an unlikely false solution (the magician can influence the spectator's choice with his gesture) before the presentation of a card trick can prevent participants from finding the real (more obvious) secret of a trick, even if they are invited to search for an alternative solution.

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

    Science.gov (United States)

    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.

  12. Monte Carlo simulations of self-assembling star-block copolymers in dilute solutions

    NARCIS (Netherlands)

    patti, A

    2010-01-01

    Computer simulations have been performed to analyze the aggregation behavior in dilute solutions of star-block copolymers of the type (AB)n in a selective solvent for the B block. We found spontaneous aggregation of single stars and formation of roughly spherical aggregates. By changing the solvopho

  13. Actuation and ion transportation of polyelectrolyte gels

    Science.gov (United States)

    Hong, Wei; Wang, Xiao

    2010-04-01

    Consisting of charged network swollen with ionic solution, polyelectrolyte gels are known for their salient characters including ion exchange and stimuli responsiveness. The active properties of polyelectrolyte gels are mostly due to the migration of solvent molecules and solute ions, and their interactions with the fixed charges on the network. In this paper, we extend the recently developed nonlinear field theory of polyelectrolyte gels by assuming that the kinetic process is limited by the rate of the transportation of mobile species. To study the coupled mechanical deformation, ion migration, and electric field, we further specialize the model to the case of a laterally constrained gel sheet. By solving the field equations in two limiting cases: the equilibrium state and the steady state, we calculate the mechanical responses of the gel to the applied electric field, and study the dependency on various parameters. The results recover the behavior observed in experiments in which polyelectrolyte gels are used as actuators, such as the ionic polymer metal composite. In addition, the model reveals the mechanism of the selectivity in ion transportation. Although by assuming specific material laws, the reduced system resembles those in most existing models in the literature, the theory can be easily generalized by using more realistic free-energy functions and kinetic laws. The adaptability of the theory makes it suitable for studying many similar material systems and phenomena.

  14. Organisation and shape of micellar solutions of block-copolymers

    NARCIS (Netherlands)

    Gaspard, J.P.; Creutz, S.; Bouchat, P.; Jerome, R.; Cohen Stuart, M.A.

    1997-01-01

    Diblock copolymers of polymethacrylic acid sodium salt, forming the hair, and styrene derivatives have been studied in aqueous solutions by SANS and SAXS. The influence of both the chemical nature and the length of the hydrophobic bloxk on the size and shape of micelles have been investigated. The m

  15. Adsorbed polyelectrolyte coatings decrease Fe(0) nanoparticle reactivity with TCE in water: conceptual model and mechanisms.

    Science.gov (United States)

    Phenrat, Tanapon; Liu, Yueqiang; Tilton, Robert D; Lowry, Gregory V

    2009-03-01

    The surfaces of reactive nanoscale zerovalent iron (NZVI) particles used for in situ groundwater remediation are modified with polymers or polyelectrolytes to enhance colloidal stability and mobility in the subsurface. However, surface modification decreases NZVI reactivity. Here, the TCE dechlorination rate and reaction products are measured as a function of adsorbed polyelectrolyte mass for three commercially available polyelectrolytes used for NZVI surface modification including poly(styrene sulfonate) (PSS), carboxymethyl cellulose (CMC), and polyaspartate (PAP). The adsorbed mass, extended layer thickness, and TCE-polyelectrolyte partition coefficient are measured and used to explain the effect of adsorbed polyelectrolyte on NZVI reactivity. For all modifiers, the dechlorination rate constant decreased nonlinearly with increasing surface excess, with a maximum of a 24-fold decrease in reactivity. The TCE dechlorination pathways were not affected. Consistent with Scheutjens-Fleer theory for homopolymer adsorption, the nonlinear relationship between the dechlorination rate and the surface excess of adsorbed polyelectrolyte suggests that adsorbed polyelectrolyte decreases reactivity primarily by blocking reactive surface sites at low surface excess where they adsorb relatively flat onto the NZVI surface, and by a combination of site blocking and decreasing the aqueous TCE concentration at the NZVI surface due to partitioning of TCE to adsorbed polyelectrolytes. This explanation is also consistent with the effect of adsorbed polyelectrolyte on acetylene formation. This conceptual model should apply to other medium and high molecular weight polymeric surface modifiers on nanoparticles, and potentially to adsorbed natural organic matter.

  16. Anisotropic Diffusion of Polyelectrolyte Chains within Multi-layer Films

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Li [Stevens Institute of Technology, Hoboken, New Jersey; Kozlovskaya, Veronika [University of Alabama, Birmingham; Kharlampieva, Eugenia [University of Alabama, Birmingham; Ankner, John Francis [ORNL; Sukhishvili, Prof. Svetlana A. [Stevens Institute of Technology, Hoboken, New Jersey

    2012-01-01

    We found diffusion of polyelectrolyte chains within multilayer films to be highly anisotropic, with the preferential chain motion parallel to the substrate. The degree of anisotropy was quantified by a combination of fluorescence recovery after photobleaching and neutron reflectometry, probing chain diffusion in directions parallel and perpendicular to the substrate, respectively. Chain mobility was controlled by ionic strength of annealing solutions and steric hindrance to ionic pairing of interacting polyelectrolytes.

  17. Complexation Behavior of Polyelectrolytes and Polyampholytes

    KAUST Repository

    Narayanan Nair, Arun Kumar

    2017-07-25

    We perform grand canonical Monte Carlo simulations to study the pH titrations of isolated polyampholytes and polyelectrolyte-polyampholyte complexes in dilute solutions. Our simulations indicate that the electrostatic interactions promote the coexistence of opposite charges along the polyampholyte chain during titration. The repulsion between excess charges typically dominates the electrostatic interaction and leads to polymer stretching. Salt ions can screen the repulsion between excess charges as well as the fluctuation-induced attraction between opposite charges, and therefore make the variation between titration curves of polyampholytes and the ideal (no electrostatic interactions) curves less significant. We observe that this screening of charge repulsion decreases the chain size. The presence of pearl-necklace configuration of polyampholytes is diminished by the addition of salt. Similar simulations for the polyelectrolyte-polyampholyte system show that the resulting complexes are generally stable in the low pH region. In comparison to ideal case, electrostatic interactions strongly influence the acid-base properties of polyampholyte chains in the adsorbed state by reducing the presence of the coexistence domain of both positive and negative charges in the titration curves. We attribute the complex formation between polyelectrolyte and polyampholyte chains in the high pH region to, e.g., the high salt content. The pH variation leads to abrupt transition between adsorbed and desorbed states. Independent of charge sequence, a polyampholyte chain in a complex is usually located at one of the ends of the polyelectrolyte chain.

  18. Polyelectrolytes-promoted Forward Osmosis Processes

    KAUST Repository

    Ge, Q.C.

    2012-11-07

    The development of the forward osmosis (FO) process has been constrained by the slow development of appropriate draw solutions. Two significant concerns related to draw solutions are the draw solute leakage and intensive-energy requirement in recycling draw solutes after the FO process. FO would be much attractive if there is no draw solute leakage and the recycle of draw solutes is easy and economic.In this study, polyelectrolytes of a series of polyacrylic acid sodium salts (PAA-Na), were explored as draw solutes in the FO process. The characteristics of high solubility in water and flexibility in structural configuration ensure the suitability of PAA-Na as draw solutes and their relative ease in recycle through pressure-driven ultrafiltration (UF) membrane processes. The high water flux with insignificant salt leakage in the FO process and the high salt rejection in UF recycle processes reveal the superiority of PAA-Na to conventional ionic salts, such as NaCl, when comparing their FO performance via the same membranes. The repeatable performance of PAA-Na after recycle indicates the absence of any aggregation problems. The overall performance demonstrates that polyelectrolytes of PAA-Na series are promising as draw solutes, and the new concept of using polyelectrolytes as draw solutes in FO processes is applicable. The magnetic nanoparticle draw solutes can generate reasonably high osmotic pressure in FO system due to the functional groups on the nanoparticles surface and they can be regenerated through magnetic field and reused as draw solutes. Thermo-responsive magnetic nanoparticles are able to be regenerated with high efficiency as the thermo-responsive property can assist the regeneration in a low-strength magnetic field.

  19. Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations.

    Science.gov (United States)

    Ou, Zhaoyang; Muthukumar, M

    2006-04-21

    We report a systematic study by Langevin dynamics simulation on the energetics of complexation between two oppositely charged polyelectrolytes of same charge density in dilute solutions of a good solvent with counterions and salt ions explicitly included. The enthalpy of polyelectrolyte complexation is quantified by comparisons of the Coulomb energy before and after complexation. The entropy of polyelectrolyte complexation is determined directly from simulations and compared with that from a mean-field lattice model explicitly accounting for counterion adsorption. At weak Coulomb interaction strengths, e.g., in solvents of high dielectric constant or with weakly charged polyelectrolytes, complexation is driven by a negative enthalpy due to electrostatic attraction between two oppositely charged chains, with counterion release entropy playing only a subsidiary role. In the strong interaction regime, complexation is driven by a large counterion release entropy and opposed by a positive enthalpy change. The addition of salt reduces the enthalpy of polyelectrolyte complexation by screening electrostatic interaction at all Coulomb interaction strengths. The counterion release entropy also decreases in the presence of salt, but the reduction only becomes significant at higher Coulomb interaction strengths. More significantly, in the range of Coulomb interaction strengths appropriate for highly charged polymers in aqueous solutions, complexation enthalpy depends weakly on salt concentration and counterion release entropy exhibits a large variation as a function of salt concentration. Our study quantitatively establishes that polyelectrolyte complexation in highly charged Coulomb systems is of entropic origin.

  20. Structure of Block Copolymer Hydrogel Formed by Complex Coacervate Process

    Science.gov (United States)

    Choi, Soohyung; Ortony, Julia; Krogstad, Daniel; Spruell, Jason; Lynd, Nathaniel; Han, Songi; Kramer, Edward

    2012-02-01

    Complex coacervation occurs when oppositely charged polyelectrolytes associate in solution, forming dense micron-sized droplets. Hydrogels with coacervate block domains were formed by mixing two ABA and A'BA' triblock copolymer solutions in water where the A and A' blocks are oppositely charged. Small-angle neutron scattering (SANS) was used to investigate the structure of hydrogels formed by ABA triblock copolymers (A block: poly(allyl glycidyl ether) functionalized with guanidinium (A) or sulfonate (A'), B block: poly(ethylene oxide)). By using an appropriate fitting model, structural information such as coacervate core block radius and water volume fraction w can be extracted from SANS data. The results reveal that w in the coacervate core block was significantly higher than in conventional triblock copolymer hydrogels where microphase separation is driven by the hydrophobicity of the core-forming blocks.

  1. Self-Assembly of Amphiphilic Block Copolymers Containing Poly(n-octadecyl acrylate) Block in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Akiba, Isamu; Akino, Yusuke; Masunaga, Hiroyasu; Sakurai, Kazuo, E-mail: akiba@env.kitakyu-u.ac.jp

    2010-11-15

    Synchrotron small-angle X-ray scattering (SAXS) experiments were carried out for poly(acrylic acid)-block-poly(n-octadecyl acrylate) (PAA-b-PODA) and PAA-b-PODA-b-PAA micelles in aqueous solutions. SAXS results indicated that PAA-b-PODA and PAA-b-PODA-b-PAA formed core-shell micelles with disk-like morphology below melting temperature of PODA in aqueous solutions. The thickness of PAA-b-PODA (diblock copolymer) micelle was larger than that of PAA-b-PODA-b-PAA (triblock copolymer) micelle. The difference of sizes between these micelles was related to difference of molecular architectures of PAA-b-PODA and PAA-b-PODA-b-PAA. PAA-b-PODA micelle showed morphological transition from disk to spherical shape with elevating temperature. On the contrary, PAA-b-PODA-b-PAA micelle maintained disk-like shape above melting temperature, although enlargement of micelle thickness is caused.

  2. Self-Assembly of Amphiphilic Block Copolymers Containing Poly(n-octadecyl acrylate) Block in Aqueous Solution

    Science.gov (United States)

    Akiba, Isamu; Akino, Yusuke; Masunaga, Hiroyasu; Sakurai, Kazuo

    2010-11-01

    Synchrotron small-angle X-ray scattering (SAXS) experiments were carried out for poly(acrylic acid)-block-poly(n-octadecyl acrylate) (PAA-b-PODA) and PAA-b-PODA-b-PAA micelles in aqueous solutions. SAXS results indicated that PAA-b-PODA and PAA-b-PODA-b-PAA formed core-shell micelles with disk-like morphology below melting temperature of PODA in aqueous solutions. The thickness of PAA-b-PODA (diblock copolymer) micelle was larger than that of PAA-b-PODA-b-PAA (triblock copolymer) micelle. The difference of sizes between these micelles was related to difference of molecular architectures of PAA-b-PODA and PAA-b-PODA-b-PAA. PAA-b-PODA micelle showed morphological transition from disk to spherical shape with elevating temperature. On the contrary, PAA-b-PODA-b-PAA micelle maintained disk-like shape above melting temperature, although enlargement of micelle thickness is caused.

  3. Conjugated polyelectrolytes fundamentals and applications

    CERN Document Server

    Liu, Bin

    2013-01-01

    This is the first monograph to specifically focus on fundamentals and applications of polyelectrolytes, a class of molecules that gained substantial interest due to their unique combination of properties. Combining both features of organic semiconductors and polyelectrolytes, they offer a broad field for fundamental research as well as applications to analytical chemistry, optical imaging, and opto-electronic devices. The initial chapters introduce readers to the synthesis, optical and electrical properties of various conjugated polyelectrolytes. This is followed by chapters on the applica

  4. Electrostatic Self-Assembled Multilayers from Side Chain Azo Polyelectrolytes

    Institute of Scientific and Technical Information of China (English)

    庹新林; 陈峥; 邓永红; 王晓工; 刘德山

    2002-01-01

    Photoresponsive behavior and self-assembly properties of three side chain azo polyelectrolytes, poly (2-(4-phenylazophenoxy) ethanol-co-acrylic acid) (PPAPE), poly (2-(4-(4′-nitrophenylazo) phenoxy) ethanol-co-acrylic acid) (PNAPE), and poly (2-(4-(4′-ethoxyphenylazo) phenoxy) ethanol-co-acrylic acid) (PEAPE), were studied. These polyelectrolytes with different degrees of functionalization of azo chromophores were fabricated into nano-composite multilayers using two types of dipping solutions through a layer-by-layer electrostatic self-assembling process. Results show that the ratio between tetrahydrofuran (THF) and H2O significantly influences the photoresponsive behavior of PNAPE in THF-H2O mixture. The THF-H2O dipping solution, used in this work for self-assembly of hydrophobic polyelectrolytes, is proved to be as applicable as aqueous dipping solution for normal self-assembly of hydrophobic polyelectrolytes. However, significant differences in the multilayer growth between the two systems were also observed, which resulted from the remarkable difference of the existing forms of the polyelectrolytes in these two dipping solutions.

  5. Structural study of coacervation in protein-polyelectrolyte complexes

    Science.gov (United States)

    Chodankar, S.; Aswal, V. K.; Kohlbrecher, J.; Vavrin, R.; Wagh, A. G.

    2008-09-01

    Coacervation is a dense liquid-liquid phase separation and herein we report coacervation of protein bovine serum albumin (BSA) in the presence of polyelectrolyte sodium polystyrene sulfonate (NaPSS) under varying solution conditions. Small-angle neutron scattering (SANS) measurements have been performed on above protein-polyelectrolyte complexes to study the structural evolution of the process that leads to coacervation and the phase separated coacervate as a function of solution pH , protein-polyelectrolyte ratio and ionic strength. SANS study prior to phase separation on the BSA-NaPSS complex shows a fractal structure representing a necklace model of protein macromolecules randomly distributed along the polystyrene sulfonate chain. The fractal dimension of the complex decreases as pH is shifted away from the isoelectric point (˜4.7) of BSA protein, which indicates the decrease in the compactness of the complex structure due to increase in the charge repulsion between the protein macromolecules bound to the polyelectrolyte. Concentration-dependence studies of the polyelectrolyte in the complex suggest coexistence of two populations of polyelectrolytes, first one fully saturated with proteins and another one free from proteins. Coacervation phase has been obtained through the turbidity measurement by varying pH of the aqueous solution containing protein and polyelectrolyte from neutral to acidic regime to get them to where the two components are oppositely charged. The spontaneous formation of coacervates is observed for pH values less than 4. SANS study on coacervates shows two length scales related to complex aggregations (mesh size and overall extent of the complex) hierarchically branched to form a larger network. The mesh size represents the distance between cross-linked points in the primary complex, which decreases with increase in ionic strength and remains the same on varying the protein-polyelectrolyte ratio. On the other hand, the overall extent of the

  6. Solution scattering studies on a virus capsid protein as a building block for nanoscale assemblies

    NARCIS (Netherlands)

    Comellas Aragones, M.; Comellas-Aragones, Marta; Sikkema, Friso D.; Delaittre, Guillaume; Terry, Ann E.; King, Stephen M.; Visser, Dirk; Heenan, Richard K.; Nolte, Roeland J.M.; Cornelissen, Jeroen Johannes Lambertus Maria; Feiters, Martin C.

    2011-01-01

    Self-assembled protein cages are versatile building blocks in the construction of biomolecular nanostructures. Because of the defined assembly behaviour the cowpea chlorotic mottle virus (CCMV) protein is often used for such applications. Here we report a detailed solution scattering study of the

  7. Composition and solution properties of fluorinated block copolymers and their surface structures in the solid state

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late(PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization(ATRP).The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement,X-ray photoelectron spectroscopy(XPS),sum frequency generation(SFG) vibrational spectroscopy,surface tension and dynamic laser light scattering(DLS).It was found that with increasing PFMA block length,water and oil repellency de-creased,the ratio of F/C increased with increasing film depth,and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased.When the number of PFMA block units reached 10,PMMA segments were detected at the copolymer surface,which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface,which in turn affects surface structure formation during solution solidification.The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.

  8. Composition and solution properties of fluorinated block copolymers and their surface structures in the solid state

    Institute of Scientific and Technical Information of China (English)

    NI HuaGang; XUE DongWu; WANG XiaoFang; ZHANG Wei; WANG XinPing; SHEN ZhiQuan

    2009-01-01

    A series of diblock copolymers composed of methyl methacrylate and 2-perfluorooctylethyl methacry-late (PMMA144-b-PFMAn) with various PFMA block lengths were prepared by atom transfer radical po-lymerization (ATRP). The surface structures and properties of these polymers in the solid state and in solution were investigated using contact angle measurement, X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG) vibrational spectroscopy, surface tension and dynamic laser light scattering (DLS). It was found that with increasing PFMA block length, water and oil repellency de-creased, the ratio of F/C increased with increasing film depth, and the degree of ordered packing of the perfluoroalkyl side chains at the surface decreased. When the number of PFMA block units reached 10, PMMA segments were detected at the copolymer surface, which was attributed to the PFMA block length affecting molecular aggregation structure of the copolymer in the solution and the interfacial structure at the air/liquid interface, which in turn affects surface structure formation during solution solidification. The results suggest that copolymer solution properties play an important role in struc-ture formation on the solid surface.

  9. Structures of some surfactant–polyelectrolyte complexes

    Indian Academy of Sciences (India)

    Rema Krishnaswamy; V A Raghunathan; A K Sood

    2003-08-01

    Structures of complexes formed in aqueous solutions by some anionic polyelectrolytes (double and single stranded (ds and ss) DNA, poly(vinyl sulfonate) (PVS), and poly(styrene sulfonate) (PSS)) with a cationic surfactant system consisting of cetyltrimethylammonium bromide (CTAB) and sodium 3-hydroxy-2-naphthoate (SHN) have been determined using small angle X-ray diffraction. All complexes are found to have a two-dimensional (2-D) hexagonal structure at low SHN concentrations. Analysis of the diffraction data shows that the ds DNA–CTAB complex has an intercalated structure, with each DNA strand surrounded by three cylindrical micelles. On increasing SHN concentration, DNA–CTAB–SHN complexes exhibit a hexagonal-to-lamellar transition, whereas PVS complexes show a hexagonal → centered rectangular → lamellar transition. PSS complexes show yet another sequence of structures. These results indicate the significant influence of the chemical nature of the polyelectrolyte on the structure of the complexes.

  10. Polyelectrolytes from NS-novolak production waste

    Energy Technology Data Exchange (ETDEWEB)

    Bajdur, W.M.; Sulkowski, W.W. [Czestochowa Technical University, Dept. of Ergonomics and Work Protection, Czestochowa (Poland)

    2003-09-12

    The chemical modification of polymer plastic wastes into useful products, such as polyelectrolytes, could be a step toward their management. For these products to be obtained, the synthesis of amino derivatives of phenol-formaldehyde resin (NS-novolak) production waste by means of known methods was performed. Products that contained different contents of amino groups in the polymer chains and that were soluble in dilute KOH and NaOH solutions were obtained. The flocculation properties of these products were tested. Studies were conducted of mine water from the Kleofas coal mine and for water from the Czestochowa metallurgical plant blast-furnace circulation system. The amino derivatives of the phenol-formaldehyde resin waste were found to have good flocculation properties. The application of these products caused a decrease in the turbidity and concentration of the dissolved contamination and improved the quality parameters of the purified sewage. These polyelectrolytes could also be used in industrial water treatment.

  11. Lysozyme complexes with thermo- and pH-responsive PNIPAM- b-PAA block copolymer

    Science.gov (United States)

    Pippa, Natassa; Meristoudi, Anastasia; Pispas, Stergios; Demetzos, Costas

    2017-02-01

    Lysozyme is an enzyme responsible for the damage of bacterial cell walls and is abundant in a number of secretions such as tears and human milk. In the present study, we investigated the structure, the physicochemical characteristics, and the temperature-responsiveness of lysozyme complexes with poly( N-isopropylacrylamide)- b-poly(acrylic acid) block polyelectrolyte in aqueous media. A gamut of light-scattering techniques and fluorescence spectroscopy were used in order to examine the complexation process, as well as the structure, solution behavior, and temperature response of the nanosized complexes. The concentration of copolymer polyelectrolyte was kept constant. The values of the scattering intensity, I 90, which is proportional to the mass of the species in solution, increased gradually as a function of C LYS, providing proof of the occurring complexation, while the size of the nanostructures decreased. The structure of the complexes became more open as the C LYS increased. The increase of the salinity did not affect the structural characteristics of the supramolecular nanoparticulate aggregates. On the other hand, the physicochemical and structural characteristics of the complexes changed upon increasing temperature, and the changes depended on the initial ratio block polyelectrolyte/lysozyme. The knowledge on developing block polyelectrolyte/protein complexes through electrostatic interactions, obtained from this investigation, may be applied to the design of nutraceuticals.

  12. Forming Reversible Gels with Triblock Polyelectrolytes: a Field-theoretic Study

    Science.gov (United States)

    Audus, Debra; Fredrickson, Glenn

    2011-03-01

    Recently, two research groups have formed reversible gels using triblock polyelectrolytes (Lemmers et al. 2010; Hunt et al., in preparation). This gel formation is driven by a phenomenon called complex coacervation, in which two oppositely charged homopolymers in solution phase separate into a polymer rich phase, known as a coacervate, and a solution phase. If instead, the polymers are triblocks with a neutral midblock and charged end blocks, under appropriate conditions they will microphase separate into micelles with cores of coacervated charged groups and coronas of neutral midblocks. These neutral midblocks act as bridges between the micelles, thereby creating a gel. One of the advantages of forming gels in this way is that the coacervate domains, and thus the gel, can be easily tuned by varying parameters such as pH, salt concentration and temperature. In order to understand the microstructures and solution sensitivity of these reversible gels, we have numerically simulated field-theoretic models of triblock polyelectrolyte mixtures in an implicit solvent. Because coacervation is driven by charge correlations, the usual mean-field assumption fails, and it is necessary to study the model beyond the level of SCFT.

  13. Multiple solutions to dense systems in radar scattering using a preconditioned block GMRES solver

    Energy Technology Data Exchange (ETDEWEB)

    Boyse, W.E. [Advanced Software Resources, Inc., Santa Clara, CA (United States)

    1996-12-31

    Multiple right-hand sides occur in radar scattering calculations in the computation of the simulated radar return from a body at a large number of angles. Each desired angle requires a right-hand side vector to be computed and the solution generated. These right-hand sides are naturally smooth functions of the angle parameters and this property is utilized in a novel way to compute solutions an order of magnitude faster than LINPACK The modeling technique addressed is the Method of Moments (MOM), i.e. a boundary element method for time harmonic Maxwell`s equations. Discretization by this method produces general complex dense systems of rank 100`s to 100,000`s. The usual way to produce the required multiple solutions is via LU factorization and solution routines such as found in LINPACK. Our method uses the block GMRES iterative method to directly iterate a subset of the desired solutions to convergence.

  14. Water-Dispersible Silica-Polyelectrolyte Nanocomposites Prepared via Acid-Triggered Polycondensation of Silicic Acid and Directed by Polycations

    Directory of Open Access Journals (Sweden)

    Philip Overton

    2016-03-01

    Full Text Available The present work describes the acid-triggered condensation of silicic acid, Si(OH4, as directed by selected polycations in aqueous solution in the pH range of 6.5–8.0 at room temperature, without the use of additional solvents or surfactants. This process results in the formation of silica-polyelectrolyte (S-PE nanocomposites in the form of precipitate or water-dispersible particles. The mean hydrodynamic diameter (dh of size distributions of the prepared water-dispersible S-PE composites is presented as a function of the solution pH at which the composite formation was achieved. Poly(2-(dimethylaminoethyl methacrylate (PDMAEMA and block copolymers of DMAEMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA were used as weak polyelectrolytes in S-PE composite formation. The activity of the strong polyelectrolytes poly(methacryloxyethyl trimethylammonium iodide (PMOTAI and PMOTAI-b-POEGMA in S-PE formation is also examined. The effect of polyelectrolyte strength and the OEGMA block on the formation of the S-PE composites is assessed with respect to the S-PE composites prepared using the PDMAEMA homopolymer. In the presence of the PDMAEMA60 homopolymer (Mw = 9400 g/mol, the size of the dispersible S-PE composites increases with solution pH in the range pH 6.6–8.1, from dh = 30 nm to dh = 800 nm. S-PDMAEMA60 prepared at pH 7.8 contained 66% silica by mass (TGA. The increase in dispersible S-PE particle size is diminished when directed by PDMAEMA300 (Mw = 47,000 g/mol, reaching a maximum of dh = 75 nm. S-PE composites formed using PDMAEMA-b-POEGMA remain in the range dh = 20–30 nm across this same pH regime. Precipitated S-PE composites were obtained as spheres of up to 200 nm in diameter (SEM and up to 65% mass content of silica (TGA. The conditions of pH for the preparation of dispersible and precipitate S-PE nanocomposites, as directed by the five selected polyelectrolytes PDMAEMA60, PDMAEMA300, PMOTAI60, PDMAEMA60-b-POEGMA38 and

  15. Synthesis, self-assembly and photoinduced surface-relief gratings of a polyacrylate-based Azo polyelectrolyte

    Science.gov (United States)

    He, Yaning; Wang, Haopeng; Tuo, Xinlin; Deng, Wei; Wang, Xiaogong

    2004-06-01

    A polyacrylate-based azo polyelectrolyte was synthesized and characterized by the spectroscopic methods and thermal analysis. Layer-by-layer self-assembly of the azo polyelectrolyte through electrostatic adsorption was explored. By using a dipping solution of the anionic azo polyelectrolyte in anhydrous DMF, together with an aqueous solution of cationic poly(diallyldimethylammonium chloride) (PDAC), high quality multilayer films were obtained through the sequential deposition of the oppositely charged polyelectrolytes. With interfering illumination of Ar + laser beams (488 nm), significant surface-relief gratings formed on the self-assembled multiplayer films were observed.

  16. Predicting the Solution Morphology of a Sulfonated Block Copolymer in Binary Solvent Mixtures

    Science.gov (United States)

    Griffin, Philip; Salmon, Grace; Ford, Jamie; Winey, Karen

    2015-03-01

    The physicochemical properties of solvent-casted block copolymer films are highly dependent on the microscopic morphology of the solutions from which they are cast. In order to achieve macroscopically homogenous polymer solutions, binary or higher-degree solvent mixtures are often required, which introduces additional complexity in understanding the molecular level interactions that control block copolymer self-assembly in solution. Using small angle x-ray scattering, we have explored the solution morphology in ternary blends of a sulfonated pentablock copolymer in select binary solvent mixtures over a range of solvent compositions and polymer concentrations. We have found that the solution morphologies in these ternary blends depend strongly on the composition of the solvent mixture. Furthermore, we demonstrate that the solvent-composition-dependent morphologies can be accurately predicted by quantifying the polymer/solvent interactions using Hansen solubility parameters. These studies are an important step toward developing a complete and predictive understanding of the solution morphology of complex polymer/solvent mixtures.

  17. Disk-cylinder and disk-sphere nanoparticles via a block copolymer blend solution construction.

    Science.gov (United States)

    Zhu, Jiahua; Zhang, Shiyi; Zhang, Ke; Wang, Xiaojun; Mays, Jimmy W; Wooley, Karen L; Pochan, Darrin J

    2013-01-01

    Researchers strive to produce nanoparticles with complexity in composition and structure. Although traditional spherical, cylindrical and membranous, or planar, nanostructures are ubiquitous, scientists seek more complicated geometries for potential functionality. Here we report the simple solution construction of multigeometry nanoparticles, disk-sphere and disk-cylinder, through a straightforward, molecular-level, blending strategy with binary mixtures of block copolymers. The multigeometry nanoparticles contain disk geometry in the core with either spherical patches along the disk periphery in the case of disk-sphere particles or cylindrical edges and handles in the case of the disk-cylinder particles. The portions of different geometry in the same nanoparticles contain different core block chemistry, thus also defining multicompartments in the nanoparticles. Although the block copolymers chosen for the blends are important for the definition of the final hybrid particles, the control of the kinetic pathway of assembly is critical for successful multigeometry particle construction.

  18. Polyelectrolyte (PE) induced interactions between Charged and zwitterionic Colloids

    Science.gov (United States)

    Pryamitsyn, Victor; Ganesan, Venkat

    2014-03-01

    A numerical self-consistent field (SCF) theory approach was developed for studying mixture of polyelectrolytes with charged and uncharged nanoparticles. Such an approach was used to analyze within the mean-field limit the polyelectrolyte-mediated effective interactions between the particles. The system considered allows for the local PE and particle charges to be defined by the local concentration of ionizable on groups on the particles and polyelectrolytes, ambient conditions like pH and the local electrostatic potential. Calculation of the free energy of a system of one, two and three particles in the polyelectrolyte solution allowdd us to calculate the particle insertion free energy, two and three body particle-particle interactions as a function of the properties of solution, polymer-particle interactions and the particle size. For the situation involving acidic PE and a base type positively charged particles, the PE mediated particle-particle interaction is purely repulsive for the larger particle-particle distances at low polymer concentrations. At short-particle particle distances and/or higher polyelectrolyte concentrations the particle-particle interaction becomes a depletion-type attraction. For Zwitterionic positively chaged paticles particles we have found a a range

  19. Self-assembly of poly(vinylidene fluoride–polystyrene block copolymers in solution: Effects of the length of polystyrene block and solvent compositions

    Directory of Open Access Journals (Sweden)

    Yao Wu

    2017-09-01

    Full Text Available We report the first preliminary and extensive study on the solution self-assembly behaviors of poly(vinylidene fluoride–b-polystyrene (PVDF–PS block copolymers. The two PVDF–PS polymers we examined have the same length of PVDF block with number averaged repeating unit of 180, but distinctly different lengths of PS block with number averaged repeating unit of 125 and 1202. The self-assembly experiments were carried out in a series of mixture solutions containing a good solvent N,N-dimethylformamide and a selective solvent with different ratios. Our results showed that the self-assembly process was greatly affected by the two factors we examined, i.e. the length of the PS block and the solvent composition. We hope that our study could stimulate more research on the self-assembly of PVDF-containing polymers in solution.

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

    Science.gov (United States)

    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.

  1. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming

    2013-01-01

    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  2. A solution for applying IEC 61499 function blocks in the development of substation automation systems

    OpenAIRE

    Vlad, Valentin; Popa, Cezar D.; Turcu, Corneliu O.; Buzduga, Corneliu

    2015-01-01

    This paper presents a solution for applying IEC 61499 function blocks along with IEC 61850 specifications in modeling and implementing control applications for substations automation. The IEC 61499 artifacts are used for structuring the control logic, while the IEC 61850 concepts for communication and information exchange between the automation devices. The proposed control architecture was implemented and validated in a simple fault protection scenario with simulated power equipment.

  3. Field-Theoretic Studies of Nanostructured Triblock Polyelectrolyte Gels

    Science.gov (United States)

    Audus, Debra; Fredrickson, Glenn

    2012-02-01

    Recently, experimentalists have developed nanostructured, reversible gels formed from triblock polyelectrolytes (Hunt et al. 2011, Lemmers et al. 2010, 2011). These gels have fascinating and tunable properties that reflect a heterogeneous morphology with domains on the order of tens of nanometers. The complex coacervate domains, aggregated oppositely charged end-blocks, are embedded in a continuous aqueous matrix and are bridged by uncharged, hydrophilic polymer mid-blocks. We report on simulation studies that employ statistical field theory models of triblock polyelectrolytes, and we explore the equilibrium self-assembly of these remarkable systems. As the charge complexation responsible for the formation of coacervate domains is driven by electrostatic correlations, we have found it necessary to pursue full ``field-theoretic simulations'' of the models, as opposed to the familiar self-consistent field theory approach. Our investigations have focused on morphological trends with mid- and end-block lengths, polymer concentration, salt concentration and charge density.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Weitao, E-mail: weitao_zhou@yahoo.com [Key Laboratory of Functional Textiles, The Education Department of Henan Province, Zhongyuan University of Technology, Zhengzhou 450007 (China); Huang, Haitao [School of Textile, Henan Institute of Engineering, Zhengzhou 451191 (China); Du, Shan [Australian Future Fibers Research and Innovation Centre for Frontier Materials, Deakin University, Geelong, VIC 3217 (Australia); Huo, Yingdong; He, Jianxin [Key Laboratory of Functional Textiles, The Education Department of Henan Province, Zhongyuan University of Technology, Zhengzhou 450007 (China); Cui, Shizhong, E-mail: snowballer@163.com [Key Laboratory of Functional Textiles, The Education Department of Henan Province, Zhongyuan University of Technology, Zhengzhou 450007 (China)

    2015-08-01

    Graphical abstract: - Highlights: • Polyethylenimine coated silk fibroin nanofibrous nonwovens were fabricated. • The characteristics such as the fiber shape and porous structure were well maintained. • The structure and adsorption properties were studied. The adsorption property for copper ions is good. - Abstract: 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 Cu{sup 2+} 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.

  5. Micellar Packing in Aqueous Solutions of As-Received and Pure Pluronic Block Copolymers

    Science.gov (United States)

    Ryu, Chang; Park, Han Jin

    2013-03-01

    Pluronic block copolymers (Pluronics) are produced on a commercial scale to enable wide range of novel applications from emulsification and colloidal stabilization as nonionic surfactants. While the Pluronic block copolymers offer the advantages of being readily available for such applications, it contains non-micellizable low molecular weight (MW) impurities that would interfere with the self-assembly and micellar packing of PEO-PPO-PEO triblock copolymers in aqueous solutions. The impacts of the low MW impurities will be discussed on the micellar packing of Pluronics F108 and F127 solutions, which form BCC and FCC. While as-received Pluronic samples typically contain about 20 wt.% low MW impurities, we were able to reduce the impurity level to less than 2 wt.% using our large scale purification technique. Comparative studies on small angle x-ray scattering (SAXS) experiments on as-received and purified Pluronics solutions revealed that the contents of triblock copolymers in solutions essentially governs the inter-micellar distance of Pluronic cubic structures. A universal relationship between triblock copolymer concentration and SAXS-based domain spacing has been finally discussed. Funding from Agency for Defense Development, Korea.

  6. Studies on the spread of local anaesthetic solution in transversus abdominis plane blocks.

    Science.gov (United States)

    Carney, J; Finnerty, O; Rauf, J; Bergin, D; Laffey, J G; Mc Donnell, J G

    2011-11-01

    The extent of analgesia provided by transversus abdominis plane blocks depends upon the site of injection and pattern of spread within the plane. There are currently a number of ultrasound-guided approaches in use, including an anterior oblique-subcostal approach, a mid-axillary approach and a more recently proposed posterior approach. We wished to determine whether the site of injection of local anaesthetic into the transversus abdominis plane affects the spread of the local anaesthetic within that plane, by studying the spread of a local anaesthetic and contrast solution in four groups of volunteers. The first group underwent the classical landmark-based transversus abdominis plane block whereby two different volumes of injectate were studied: 0.3 ml.kg(-1) vs 0.6 ml.kg(-1). The second group underwent transversus abdominis plane block using the anterior subcostal approach. The third group underwent transversus abdominis plane block using the mid-axillary approach. The fourth group underwent transversus abdominis plane block using the posterior approach, in which local anaesthetic was deposited close to the antero-lateral border of the quadratus lumborum. All volunteers subsequently underwent magnetic resonance imaging at 1, 2 and 4 h following each block to determine the spread of local anaesthetic over time. The studies demonstrated that the anterior subcostal and mid-axillary ultrasound approaches resulted in a predominantly anterior spread of the contrast solution within the transversus abdominis plane and relatively little posterior spread. There was no spread to the paravertebral space with the anterior subcostal approach. The mid-axillary transversus abdominis plane block gave faint contrast enhancement in the paravertebral space at T12-L2. In contrast, the posterior approaches, using both landmark and ultrasound identifications, resulted in predominantly posterior spread of contrast around the quadratus lumborum to the paravertebral space from T5 to L1

  7. Sonication-assisted synthesis of polyelectrolyte-coated curcumin nanoparticles.

    Science.gov (United States)

    Zheng, Zhiguo; Zhang, Xingcai; Carbo, Daniel; Clark, Cheryl; Nathan, Cherie-Ann; Lvov, Yuri

    2010-06-01

    A new method of nanoparticle formulation for poorly water-soluble materials was demonstrated for curcumin. The drug was dissolved in organic solvent that is miscible with water (ethanol), and drug nucleation was initiated by gradual worsening of the solution by the addition of an aqueous polyelectrolyte assisted by ultrasonication. Curcumin crystals of 60-100 nm size were obtained depending on the component concentrations, sonication power, and initial solvent. Layer-by-layer shell assembly with biocompatible polyelectrolytes was used to provide a particle coating with a high surface potential and the stabilization of drug nanocolloids. Polyelectrolyte layer-by-layer encapsulation allowed sustained drug release from nanoparticles over the range of 10-20 h.

  8. Exact solution of corner-modified banded block-Toeplitz eigensystems

    Science.gov (United States)

    Cobanera, Emilio; Alase, Abhijeet; Ortiz, Gerardo; Viola, Lorenza

    2017-05-01

    Motivated by the challenge of seeking a rigorous foundation for the bulk-boundary correspondence for free fermions, we introduce an algorithm for determining exactly the spectrum and a generalized-eigenvector basis of a class of banded block quasi-Toeplitz matrices that we call corner-modified. Corner modifications of otherwise arbitrary banded block-Toeplitz matrices capture the effect of boundary conditions and the associated breakdown of translational invariance. Our algorithm leverages the interplay between a non-standard, projector-based method of kernel determination (physically, a bulk-boundary separation) and families of linear representations of the algebra of matrix Laurent polynomials. Thanks to the fact that these representations act on infinite-dimensional carrier spaces in which translation symmetry is restored, it becomes possible to determine the eigensystem of an auxiliary projected block-Laurent matrix. This results in an analytic eigenvector Ansatz, independent of the system size, which we prove is guaranteed to contain the full solution of the original finite-dimensional problem. The actual solution is then obtained by imposing compatibility with a boundary matrix, whose shape is also independent of system size. As an application, we show analytically that eigenvectors of short-ranged fermionic tight-binding models may display power-law corrections to exponential behavior, and demonstrate the phenomenon for the paradigmatic Majorana chain of Kitaev.

  9. Ionizable polyelectrolyte brushes: brush height and electrosteric interaction

    NARCIS (Netherlands)

    Biesheuvel, P.M.

    2004-01-01

    Semi-analytical scaling theory is used to describe quenched and annealed (weakly charged, ionizable, charge-regulating) polyelectrolyte brushes in electrolyte solutions of arbitrary salt concentration. An Alexander-De Gennes box model with homogeneous distribution of polymer segments and the free en

  10. Terminal groups control self-assembly of amphiphilic block copolymers in solution

    Science.gov (United States)

    Grzelakowski, M.; Kita-Tokarczyk, K.

    2016-03-01

    The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability.The terminal groups of amphiphilic block copolymers are shown to control macromolecular self-assembly in aqueous solutions, in the micellar/lamellar region of the phase diagram. At the same concentration and using the same self-assembly conditions, dramatic differences are observed in polymer hydration and the resulting nano-/microstructure for two series of polymers with identical block chemistry and hydrophilic-lipophilic balance (HLB). This suggests a strong contribution from end groups to the hydration as the initial step of the self-assembly process, and could be conveniently used to guide the particle morphology and size. Additionally, for polymers with those head groups which drive vesicular structures, differences in membrane organization affect their physical properties, such as permeability. Electronic supplementary information (ESI) available: Fig. S1: Particle diameters for hydrated NH2-ABA-NH2 polymers with different degrees of functionalization; Fig. S2: TEM characterization of compound micelles from BA-OH polymer after extrusion; Fig. S3: Cryo-TEM and stopped flow characterization of lipid vesicles; Fig. S4 and S5: NMR spectra for ABA and BA polymers

  11. Error bounds on block Gauss-Seidel solutions of coupled multiphysics problems

    KAUST Repository

    Whiteley, J. P.

    2011-05-09

    Mathematical models in many fields often consist of coupled sub-models, each of which describes a different physical process. For many applications, the quantity of interest from these models may be written as a linear functional of the solution to the governing equations. Mature numerical solution techniques for the individual sub-models often exist. Rather than derive a numerical solution technique for the full coupled model, it is therefore natural to investigate whether these techniques may be used by coupling in a block Gauss-Seidel fashion. In this study, we derive two a posteriori bounds for such linear functionals. These bounds may be used on each Gauss-Seidel iteration to estimate the error in the linear functional computed using the single physics solvers, without actually solving the full, coupled problem. We demonstrate the use of the bound first by using a model problem from linear algebra, and then a linear ordinary differential equation example. We then investigate the effectiveness of the bound using a non-linear coupled fluid-temperature problem. One of the bounds derived is very sharp for most linear functionals considered, allowing us to predict very accurately when to terminate our block Gauss-Seidel iteration. © 2011 John Wiley & Sons, Ltd.

  12. Water activity of aqueous solutions of ethylene oxide-propylene oxide block copolymers and maltodextrins

    Directory of Open Access Journals (Sweden)

    N. D. D. Carareto

    2010-03-01

    Full Text Available The water activity of aqueous solutions of EO-PO block copolymers of six different molar masses and EO/PO ratios and of maltodextrins of three different molar masses was determined at 298.15 K. The results showed that these aqueous solutions present a negative deviation from Raoult's law. The Flory-Huggins and UNIFAC excess Gibbs energy models were employed to model the experimental data. While a good agreement was obtained with the Flory-Huggins equation, discrepancies were observed when predicting the experimental behavior with the UNIFAC model. The water activities of ternary systems formed by a synthetic polymer, maltodextrin and water were also measured and used to test the predictive capability of both models.

  13. Competitive reactions in solutions of poly-L-histidine, calf thymus DNA, and synthetic polyanions: determining the binding constants of polyelectrolytes.

    Science.gov (United States)

    Zelikin, Alexander N; Trukhanova, Elizabeth S; Putnam, David; Izumrudov, Vladimir A; Litmanovich, Andrey A

    2003-11-12

    The physicochemical characteristics of a nonviral gene delivery system will govern its functional bioactivity; however, empiricism dominates the literature in this field, and a significant deficiency of quantitative investigation and evaluation of nonviral gene delivery vehicles remains. Herein, we derive a physical model and experimental method to quantitatively determine the binding constants between a model polycationic nonviral gene delivery vehicle poly-L-histidine (PLH) and calf thymus DNA. The approach has utility to a variety of systems and is not limited to the described polymer model. The interaction of PLH with DNA was monitored by fluorescence quenching of an ethidium bromide probe in the pH range 4 to 8. The interaction increased with pH decrease with the most pronounced change between pH 6 and 7. The obtained pH-dependence of fraction of salt bonds formed between PLH and DNA was used to estimate pK(a) of PLH in the presence of DNA, which equaled 6.24. The interaction of PLH with DNA in the presence of added synthetic polyanions was studied by the same approach and found to be controlled by pH, nature of the charge groups of the polyanion, and its degree of polymerization. In the mixture with sodium poly(styrenesulfonate) the interaction was negligible in the whole studied pH range, whereas in the mixtures with sodium poly(acrylate) (PA) or sodium poly(methacrylate), DNA was able to compete effectively for the binding with PLH. For PA samples with degree of polymerization higher than degree of polymerization of PLH, DP(PA) > DP(PLH), the fraction of polycation bound to DNA was constant regardless of DP(PA.) In contrast, at DP(PA) PLH), a pronounced increase in the bound fraction was observed. It substantiates the notion that the binding energy of two polymers is mainly controlled by the DP of the shorter component of polyelectrolyte complex. The data on PLH distribution between DNA and added polyanion with different values of DP were treated according

  14. Hydroplaning of subaqueous debris flows and glide blocks: Analytical solutions and discussion

    Science.gov (United States)

    Harbitz, Carl B.; Parker, Gary; ElverhøI, Anders; Marr, Jeffrey G.; Mohrig, David; Harff, Peter A.

    2003-07-01

    Subaqueous debris flows often attain significantly higher velocities and longer run-out distances than their subaerial counterparts in spite of increased viscous drag and reduced effective gravity due to buoyancy. Recent experimental research suggests that a basal lubricating layer of water associated with hydroplaning decouples the sediments from the bed, resulting in a dramatic reduction of the basal shear stress. Hydroplaning thus provides an explanation for these observations. The conditions for onset of hydroplaning are discussed in terms of critical densimetric Froude number. The stress reduction due to a lubricating layer of water or mud slurry is studied via equilibrium solutions for a two-layer Couette flow. The calculations reveal that the stresses in both the low-viscosity lubricating layer and the high-viscosity deforming deposits below it are substantially reduced. The principles of laminar boundary layers are used to develop an equilibrium solution for the steady motion of a hydroplaning debris glide block. This adjusted version of lubrication theory properly accounts for hydroplaning associated with a dynamic pressure generated at the head of the block. Example calculations at both laboratory and field scale support the experimental results of reduced bed friction, limited erosion, sediment rheology independence, and high velocities. The results also reveal the possibility for a net up-slope discharge in the lubricating layer.

  15. Meso-scale Modeling of Block Copolymers Self-Assembly in Casting Solutions for Membrane Manufacture

    KAUST Repository

    Moreno Chaparro, Nicolas

    2016-05-01

    Isoporous membranes manufactured from diblock copolymer are successfully produced at laboratory scale under controlled conditions. Because of the complex phenomena involved, membrane preparation requires trial and error methodologies to find the optimal conditions, leading to a considerable demand of resources. Experimental insights demonstrate that the self-assembly of the block copolymers in solution has an effect on the final membrane structure. Nevertheless, the complete understanding of these multi-scale phenomena is elusive. Herein we use the coarse-grained method Dissipative Particle Dynamics to study the self-assembly of block copolymers that are used for the preparation of the membranes. To simulate representative time and length scales, we introduce a framework for model reduction of polymer chain representations for dissipative particle dynamics, which preserves the properties governing the phase equilibria. We reduce the number of degrees of freedom by accounting for the correlation between beads in fine-grained models via power laws and the consistent scaling of the simulation parameters. The coarse-graining models are consistent with the experimental evidence, showing a morphological transition of the aggregates as the polymer concentration and solvent affinity change. We show that hexagonal packing of the micelles can occur in solution within different windows of polymer concentration depending on the solvent affinity. However, the shape and size dispersion of the micelles determine the characteristic arrangement. We describe the order of crew-cut micelles using a rigid-sphere approximation and propose different phase parameters that characterize the emergence of monodisperse-spherical micelles in solution. Additionally, we investigate the effect of blending asymmetric diblock copolymers (AB/AC) over the properties of the membranes. We observe that the co-assembly mechanism localizes the AC molecules at the interface of A and B domains, and induces

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

    Energy Technology Data Exchange (ETDEWEB)

    Nap, R. J.; Tagliazucchi, M.; Szleifer, I., E-mail: igalsz@northwestern.edu [Department of Biomedical Engineering, Department of Chemistry, and Chemistry of Life Processes Institute, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3100 (United States)

    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

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

    Science.gov (United States)

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

    2014-01-01

    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

  18. In situ gelling stimuli-sensitive block copolymer hydrogels for drug delivery.

    Science.gov (United States)

    He, Chaoliang; Kim, Sung Wan; Lee, Doo Sung

    2008-05-08

    Stimuli-sensitive block copolymer hydrogels, which are reversible polymer networks formed by physical interactions and exhibit a sol-gel phase-transition in response to external stimuli, have great potential in biomedical and pharmaceutical applications, especially in site-specific controlled drug-delivery systems. The drug may be mixed with a polymer solution in vitro and the drug-loaded hydrogel can form in situ after the in vivo administration, such as injection; therefore, stimuli-sensitive block copolymer hydrogels have many advantages, such as simple drug formulation and administration procedures, no organic solvent, site-specificity, a sustained drug release behavior, less systemic toxicity and ability to deliver both hydrophilic and hydrophobic drugs. Among the stimuli in the biomedical applications, temperature and pH are the most popular physical and chemical stimuli, respectively. The temperature- and/or pH-sensitive block copolymer hydrogels for biomedical applications have been extensively developed in the past decade. This review focuses on recent development of the preparation and application for drug delivery of the block copolymer hydrogels that respond to temperature, pH or both stimuli, including poly(N-substituted acrylamide)-based block copolymers, poloxamers and their derivatives, poly(ethylene glycol)-polyester block copolymers, polyelectrolyte-based block copolymers and the polyelectrolyte-modified thermo-sensitive block copolymers. In addition, the hydrogels based on other stimuli-sensitive block copolymers are discussed.

  19. Key considerations in the determination of polyelectrolyte concentration by the colloidal titration method

    Directory of Open Access Journals (Sweden)

    Miguel A. Zanuttini

    2007-01-01

    Full Text Available Medium or high charge density cationic polyelectrolytes are frequently used for water treatment. In the papermaking wet-end they are used as retention agents or as flocculating aids. Negative polyelectrolytes that enter the papermaking system increase the demand for cationic poly-electrolytes. Polyelectrolyte concentration can be determined by the colloidal titration method, using either of two options for detecting the endpoint: i visual observation or spectrophotometric determination of the colour change of an indicator, or ii streaming current measurement. This work discusses the best conditions for the application of the titration using spectrophotometric measurement for the end point detection. Poly-diallyldimethylammonium chloride was used as the cationic polyelec-trolyte, potassium polyvinyl sulphate as the negative polyelectrolyte, and o-toluidine blue as the positive indicator dye. The polyelectrolyte concen-tration range, interference from the metal ions affecting the indicator color change, the optimal indicator concentration to avoid precipitation problems, and the effect of adding a surfactant to the indicator solution were also considered. Titration curves were analyzed and optimized. Under these conditions the technique provided results with acceptable precision.

  20. Controlled Release of the Indomethacin Microencapsulation Based on Layer-by-layer Assembly by Polyelectrolyte Multilayers

    Institute of Scientific and Technical Information of China (English)

    CHEN You-fang; LIN Xian-fu

    2007-01-01

    Indomethacin has been encapsulated with polyelectrolyte multilayers for controlled release. Gelatin and alginate were alternatively deposited on indomethacin microcrystals. The released amount of indomethacin from coated microcrystals in pH6. 8phosphate buffer solution (PBS) was measured with a UV spectrophometer. The polyelectrolyte multilayer capsule thickness was proved to control the release rate. The effects of osmotic pressure existed during the release process of indomethacin from microcapsules coated by (gelatin/alginate) 4.

  1. Synthesis and aqueous solution properties of novel sugar methacrylate-based homopolymers and block copolymers.

    Science.gov (United States)

    Narain, Ravin; Armes, Steven P

    2003-01-01

    We report the facile preparation of a range of novel, well-defined cyclic sugar methacrylate-based polymers without recourse to protecting group chemistry. 2-Gluconamidoethyl methacrylate (GAMA) and 2-lactobionamidoethyl methacrylate (LAMA) were prepared directly by reacting 2-aminoethyl methacrylate with D-gluconolactone and lactobionolactone, respectively. Homopolymerization of GAMA and LAMA by atom transfer radical polymerization (ATRP) gave reasonably low polydispersities as judged by aqueous gel permeation chromatography. A wide range of sugar-based block copolymers were prepared using near-monodisperse macroinitiators based on poly(ethylene oxide) [PEO], poly(propylene oxide) [PPO], or poly(e-caprolactone) [PCL] and/or by sequential monomer addition of other methacrylic monomers such as 2-(diethylamino)ethyl methacrylate [DEA], 2-(diisopropylaminoethyl methacrylate [DPA], or glycerol monomethacrylate [GMA]. The reversible micellar self-assembly of selected sugar-based block copolymers [PEO23-GAMA50-DEA100, PEO23-LAMA30-DEA50, PPO33-GAMA50, and PPO33-LAMA50] was studied in aqueous solution as a function of pH and temperature using dynamic light scattering, transmission electron microscopy, surface tensiometry, and 1H NMR spectroscopy.

  2. Bilayer membrane permeability of ionic liquid-filled block copolymer vesicles in aqueous solution.

    Science.gov (United States)

    Bai, Zhifeng; Zhao, Bin; Lodge, Timothy P

    2012-07-19

    The bilayer membrane permeability of block copolymer vesicles ("polymersomes") with ionic liquid interiors dispersed in water is quantified using fluorescence quenching. Poly((1,2-butadiene)-b-ethylene oxide) (PB-PEO) block copolymer vesicles in water with their interiors filled with a common hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, were prepared containing a hydrophobic dye, Nile Red, by intact migration of dye-encapsulated vesicles from the ionic liquid to water at room temperature. A small quencher molecule, dichloroacetamide, was added to the aqueous solution of the dye-loaded vesicles, and the permeation of the quencher passing through the membrane into the interior was determined from the fluorescence quenching kinetics. Rapid permeation of the quencher across the nanoscale membrane was observed, consistent with the high fluidity of the liquid polybutadiene membrane. Two different PB-PEO copolymers were employed, in order to vary the thickness of the solvophobic membrane. A significant increase in membrane permeability was also observed with decreasing membrane thickness, which is tentatively attributable to differences in quencher solubility in the membranes. Quantitative migration of the vesicles from the aqueous phase back to an ionic liquid phase was achieved upon heating. These microscopically heterogeneous and thermoresponsive vesicles with permeable and robust membranes have potential as recyclable nanoreactors, in which the high viscosity and capital expense of an ionic liquid reaction medium can be mitigated, while retaining the desirable features of ionic liquids as reaction media, and facile catalyst recovery.

  3. Digital block with or without the addition of epinephrine in the anesthetic solution.

    Science.gov (United States)

    dos Reis Júnior, Almiro; Quinto, Denise

    2016-01-01

    Review of various techniques for digital blocks with local anesthetic, with or without epinephrine. Description of various procedures and comparison of results reported in the literature, mainly on latency and quality of anesthesia, details on vasoconstrictor effect of epinephrine, intraoperative bleeding, necessity of tourniquet use, duration of anesthesia and postoperative analgesia, blood flow and digital SpO2 behavior, local and systemic complications, and also approaches and drugs to be used in certain situations of ischemia. The advantages of adding epinephrine to the anesthetic solution are minor when compared to the risks of the procedure, and it seems dangerous to use a vasoconstrictor in the fingers, unless the safety of the technique and the possibility of discarding the tourniquet are definitely proven. Copyright © 2014 Sociedade Brasileira de Anestesiologia. Published by Elsevier Editora Ltda. All rights reserved.

  4. [Digital block with or without the addition of epinephrine in the anesthetic solution].

    Science.gov (United States)

    Reis Júnior, Almiro Dos; Quinto, Denise

    2016-01-01

    Review of various techniques for digital blocks with local anesthetic, with or without epinephrine. Description of various procedures and comparison of results reported in the literature, mainly on latency and quality of anesthesia, details on vasoconstrictor effect of epinephrine, intraoperative bleeding, necessity of tourniquet use, duration of anesthesia and postoperative analgesia, blood flow and digital SpO2 behavior, local and systemic complications, and also approaches and drugs to be used in certain situations of ischemia. The advantages of adding epinephrine to the anesthetic solution are minor when compared to the risks of the procedure, and it seems dangerous to use a vasoconstrictor in the fingers, unless the safety of the technique and the possibility of discarding the tourniquet are definitely proven. Copyright © 2014 Sociedade Brasileira de Anestesiologia. Publicado por Elsevier Editora Ltda. All rights reserved.

  5. Fabrication of monodisperse magnetic nanoparticles released in solution using a block copolymer template

    Science.gov (United States)

    Morcrette, Mélissa; Ortiz, Guillermo; Tallegas, Salomé; Joisten, Hélène; Tiron, Raluca; Baron, Thierry; Hou, Yanxia; Lequien, Stéphane; Bsiesy, Ahmad; Dieny, Bernard

    2017-07-01

    This paper describes a fabrication process of monodisperse magnetic nanoparticles released in solution, based on combined ‘top-down’ and ‘bottom-up’ approaches. The process involves the use of a self-assembled PS-PMMA block copolymer formed on a sacrificial layer. Such an approach was so far mostly explored for the preparation of patterned magnetic media for ultrahigh density magnetic storage. It is here extended to the preparation of released monodisperse nanoparticles for biomedical applications. A special sacrificial layer had to be developed compatible with the copolymer self-organization. The resulting nanoparticles exhibit very narrow size dispersion (≈7%) and can be good candidates as contrast agents for medical imaging i.e. magnetic resonance imaging or magnetic particle imaging. The approach provides a great freedom in the choice of the particles shapes and compositions. In particular, they can be made of biocompatible magnetic material.

  6. Synthesis and Solution Properties of Double Hydrophilic Poly(ethylene oxide-block-poly(2-ethyl-2-oxazoline (PEO-b-PEtOx Star Block Copolymers

    Directory of Open Access Journals (Sweden)

    Felix H. Schacher

    2013-09-01

    Full Text Available We demonstrate the synthesis of star-shaped poly(ethylene oxide-block-poly(2-ethyl-2-oxazoline [PEOm-b-PEtOxn]x block copolymers with eight arms using two different approaches, either the “arm-first” or the “core-first” strategy. Different lengths of the outer PEtOx blocks ranging from 16 to 75 repeating units were used, and the obtained materials [PEO28-b-PEtOxx]8 were characterized via size exclusion chromatography (SEC, nuclear magnetic resonance spectroscopy (NMR, and Fourier-transform infrared spectroscopy (FT-IR measurements. First investigations regarding the solution behavior in water as a non-selective solvent revealed significant differences. Whereas materials synthesized via the “core-first” method seemed to be well soluble (unimers, aggregation occurred in the case of materials synthesized by the “arm-first” method using copper-catalyzed azide-alkyne click chemistry.

  7. Multicompartment Nanoparticles Formed by a Heparin-Mimicking Block Terpolymer in Aqueous Solutions

    NARCIS (Netherlands)

    Uchman, M.; Stepanek, M.; Prochazka, K.; Mountrichas, G.; Pispas, S.; Voets, I.K.; Walther, A.

    2009-01-01

    A new amphiphilic block. terpolymer poly((sulfamate-carboxylate)isoprene)-block-polystyrene-block-poly(ethyl ene oxide), PISC230-PS52-PEO151, with a narrow molecular weight distribution (PDI = 1.05), was synthesized via the post. polymerization reaction of the anionically prepared precursor block

  8. Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Voisin, David

    2002-07-01

    Oppositely charged surfactant and polyelectrolyte are present in hair shampoos and conditioners, together with particles (e.g. anti-dandruff agents for scalp) and droplets (e.g. silicone oil for the hair). These are normally formulated at high surfactant concentrations, beyond the flocculation region for the polyelectrolyte concentration used. However, on dilution with water, during application, flocs are formed which carry the particles and droplets to the scalp and hair. The addition of an anionic surfactant to an aqueous solution of cationic polyelectrolyte, at a given concentration, can lead to the formation of polyelectrolyte-surfactant 'particles', in which the surfactant 'binds' to the polyelectrolyte. This occurs from the critical association concentration (CAC), up to the surfactant concentration corresponding to maximum binding. Within this range of surfactant concentrations, the surfactant bound to the polyelectrolyte is thought to associate to form what might be termed 'internal micelles'. Each polyelectrolyte-surfactant particle in the region of the CAC, and just beyond, contains many polyelectrolyte chains, held together essentially by micelle bridges. These particles, however, remain net positively charged, and therefore stable. At the other end of the binding range of the surfactant, so many internal micelles are present that the polymer-surfactant particles are now net negatively charged. Indeed binding stops since no further micelles can be accommodated. Again, the particles are stable. However, there exists a range of surfactant concentrations, lying within the range referred to above, where the net charge is reduced sufficiently that the polymer-surfactant particles will flocculate to form much larger structures. The onset of this second range might be termed the 'critical flocculation concentration' (CFC), and the end, the 'critical stabilisation concentration' (CSC). In this work, the CFC and

  9. Building Highly Flexible Polyelectrolyte Nanotubes

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    @@ Flexibility of polyelectrolyte nanotubes is necessary if they are to be exploited in applications such as developing photoelectric devices with strong mechanical properties. In a recent attempt, high flexibility has been observed from such nanotubes prepared by a research team headed by Prof. Li Junbai of the CAS Institute of Chemistry (ICCAS).

  10. Comparison of three solutions to correct erroneous blocks to extract an image of a multiplicative homomorphic cryptosystem

    Science.gov (United States)

    Islam, N.; Puech, W.; Brouzet, R.

    2011-02-01

    Multiplicative homomorphic properties of a cryptosystem can be used in various applications requiring security, protection and authentication e.g. digital fingerprinting, electronic voting, on line betting etc. Secret sharing between two or more parties exploiting multiplicative homomorphic property of RSA results into erroneous blocks while extracting the message. The generation of these erroneous blocks limits the capabilities of homomorphic properties of RSA to be used in its full extend. This paper provides three different approaches as solutions to the problem of erroneous blocks in image. These solutions are: mean value approach, shortest distance approach and image preprocessing approach. It has been observed that shortest distance approach results into good PSNR but it is computationally expensive. The best approach with high PSNR is image preprocessing approach before sharing process, which results into no erroneous blocks in the extracted image, thus no extra extraction techniques are required.

  11. Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries.

    Science.gov (United States)

    Porcarelli, Luca; Shaplov, Alexander S; Salsamendi, Maitane; Nair, Jijeesh R; Vygodskii, Yakov S; Mecerreyes, David; Gerbaldi, Claudio

    2016-04-27

    Polymer electrolytes have been proposed as replacement for conventional liquid electrolytes in lithium-ion batteries (LIBs) due to their intrinsic enhanced safety. Nevertheless, the power delivery of these materials is limited by the concentration gradient of the lithium salt. Single-ion conducting polyelectrolytes represent the ideal solution since their nature prevents polarization phenomena. Herein, the preparation of a new family of single-ion conducting block copolymer polyelectrolytes via reversible addition-fragmentation chain transfer polymerization technique is reported. These copolymers comprise poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) and poly(ethylene glycol) methyl ether methacrylate blocks. The obtained polyelectrolytes show low Tg values in the range of -61 to 0.6 °C, comparatively high ionic conductivity (up to 2.3 × 10(-6) and 1.2 × 10(-5) S cm(-1) at 25 and 55 °C, respectively), wide electrochemical stability (up to 4.5 V versus Li(+)/Li), and a lithium-ion transference number close to unity (0.83). Owing to the combination of all mentioned properties, the prepared polymer materials were used as solid polyelectrolytes and as binders in the elaboration of lithium-metal battery prototypes with high charge/discharge efficiency and excellent specific capacity (up to 130 mAh g(-1)) at C/15 rate.

  12. Self-assembled polyelectrolyte nanorings observed by liquid-cell AFM

    Energy Technology Data Exchange (ETDEWEB)

    Menchaca, J-Luis [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, San Luis Potosi (Mexico); Flores, Hector [Facultad de Estomatologia, Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, San Luis Potosi (Mexico); Cuisinier, Frederic [INSERM U 595, Federation de Recherche Odontologiques, Universite Louis Pasteur, 11 rue Humann, 67085 Strasbourg Cedex (France); Perez, ElIas [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, San Luis Potosi (Mexico)

    2004-06-09

    Self-assembled polyelectrolyte nanorings formed by polyelectrolytes are presented for the first time in this work. They are formed by poly(ethylenimine) (PEI) and poly(sodium 4-styrenesulfanate) (PSS) during the two first steps of the formation of the self-assembled polyelectrolyte films (SAPFs). These are formed on a negatively charged glass surface and observed by an in situ liquid-cell AFM technique, which has recently been introduced as an alternative technique to follow polyelectrolyte multilayer formation without drying effects (Menchaca et al 2003 Colloids Surf. A 222 185). Nanoring formation strongly depends on the preparation method and parameters such as polyelectrolyte filtration, air and CO{sub 2} presence during SAPFs formation and buffer solution. A necessary condition to obtain nanorings is that polyelectrolyte solutions have to be filtered prior to injection into the liquid-cell AFM. The outer diameter of nanorings can be varied from hundreds of nanometres to microns by changing these parameters. Nanorings are stable in the liquid cell for hours but they disappear on contact with air. Additionally, carbonate ions seem to be mainly responsible for the formation of this novel structure.

  13. Parametrization of direct and soft steric-undulatory forces between DNA double helical polyelectrolytes in solutions of several different anions and cations.

    Science.gov (United States)

    Podgornik, R; Rau, D C; Parsegian, V A

    1994-04-01

    Directly measured forces between DNA helices in ordered arrays have been reduced to simple force coefficients and mathematical expressions for the interactions between pairs of molecules. The tabulated force parameters and mathematical expressions can be applied to parallel molecules or, by transformation, to skewed molecules of variable separation and mutual angle. This "toolbox" of intermolecular forces is intended for use in modelling molecular interactions, assembly, and conformation. The coefficients characterizing both the exponential hydration and the electrostatic interactions depend strongly on the univalent counterion species in solution, but are only weakly sensitive to anion type and temperature (from 5 to 50 degrees C). Interaction coefficients for the exponentially varying hydration force seen at spacings less than 10 to 15 A between surfaces are extracted directly from pressure versus interaxial distance curves. Electrostatic interactions are only observed at larger spacings and are always coupled with configurational fluctuation forces that result in observed exponential decay lengths that are twice the expected Debye-Huckel length. The extraction of electrostatic force parameters relies on a theoretical expression describing steric forces of molecules "colliding" through soft exponentially varying direct interactions.

  14. Macroion Interaction at Polyelectrolyte Brush Interfaces

    Science.gov (United States)

    Qu, Chen

    2015-03-01

    The effect of macroions, including synthetic polyelectrolytes, DNA and proteins, on the structure and surface properties of charged polymer thin films remains inadequately understood partially due to the complexity involving the hydrophobic effect and the conformational change of polymeric macroions. In this work, we explore a group of inorganic nanocluster based macroions, hydrophilic polyoxometalates (POMs) of robust nanocluster structure and carrying high surface charges (~ 2-42 negative charges) to investigate their interaction with surface tethered poly-2-vinylpyridine (P2VP) brush-like thin films immersed in aqueous solution. We observe the collapse of swollen P2VP chains by adding POM macroions of increased concentration by AFM, QCM and contact goniometer measurements, in sharp contrast to the increased chain stretching by adding monovalent salts. A careful comparison is made between distinct POMs based on their charge, size and chemical nature. These findings serve as a good reference for theoretical model modification and design of new mesoporous composite membranes.

  15. Changes of Resistance During Polyelectrolyte-enhanced Stirred Batch Ultrafiltration

    Institute of Scientific and Technical Information of China (English)

    ZHU Xin-Sheng; Kwang-Ho CHOO

    2007-01-01

    The permeation flux or the resistance in the ultrafiltration process is mainly limited by osmotic pressure,and it may originate from various kinds of polymer interactions. However, the real origin of permeation resistance hasn't been clarified yet in the light of polymer solution nature. The removal of nitrate contamination by polyelectrolytes was carried out with stirred batch ultrafiltration. The polyelectrolyte concentrations both in permeate and retentate were analyzed with total organic carbon analyzer and permeate mass was acquired by electronic balance connected with computer. The total resistance was calculated and interpreted based on the osmotic pressures in three concentration regimes. In the dilute region, the resistance was proportional to polymer concentration; in the semidilute region, the resistance depended on polymer concentration in the parabolic relationship; in the highly concentrated solution regime, the osmotic pressure factor (OPF) would dominate the total resistance; and the deviation from OPF control could come from the electrostatic repulsion between the tightly compacted and charged polyelectrolyte particles at extremely concentrated solution regime. It was first found that dilute and semidilute concentration regions can be easily detected by plotting the log-log curves of the polymer concentration versus the ratio of the total resistance to polymer concentration. The new concept OPF was defined and did work well at highly concentrated regime.

  16. Hydrophobically modified polyelectrolytes: Characterization, aggregation and adsorption

    Science.gov (United States)

    Islam, Mohammad Ferdous

    The focus of our work was to experimentally study the aggregation and adsorption behavior of model HM polyelectrolytes. Hydrophobically modified alkali soluble emulsions (HASE), the model HM polyelectrolytes, were chosen because they had complex architecture yet possessed key variables for systematic study. The HASE polymers have methacrylic acid (MAA) and ethyl acrylate (EA) in the backbone with pendent hydrophobic groups. Characterization of a single molecule is an important first step in understanding the aggregation and adsorption of these polymers. However, characterizations of the HASE polymers using conventional techniques such as gel permeation chromatography or static light scattering were difficult because of the hydrophobic association. In this study, two different approaches have been taken to prevent the hydrophobic association in aqueous solution: (1) hydrolyze the polymer to cleave the hydrophobic constituents, and (2) use methyl beta-cyclodextrin that has a hydrophobic cavity and a hydrophilic outer shell, to shield the hydrophobes from associating. By taking these two approaches and using gel permeation chromatography (GPC), dynamic (DLS) and static (SLS) light scattering techniques, the molecular weight, hydrodynamic radius and radius of gyration of a single molecule were determined. Except for one chemical site, we were able to determine that branching or grafting did not occur in the polymer chain during synthesis. Our aggregation studies showed that, in aqueous solutions, the HASE polymers formed small aggregates (presumably single micelles of single or a few chains) and large aggregates (presumably formed by bridging between micelles). The radii and masses of the larger aggregates, measured using DLS and SLS, were found to increase with an increase in the polymer concentration, indicating an open association process for the HASE polymers. Our SLS results also showed that, at high salt concentration, the aggregates of the HASE polymer with

  17. Complexation and coacervation of like-charged polyelectrolytes inspired by mussels.

    Science.gov (United States)

    Kim, Sangsik; Huang, Jun; Lee, Yongjin; Dutta, Sandipan; Yoo, Hee Young; Jung, Young Mee; Jho, YongSeok; Zeng, Hongbo; Hwang, Dong Soo

    2016-02-16

    It is well known that polyelectrolyte complexes and coacervates can form on mixing oppositely charged polyelectrolytes in aqueous solutions, due to mainly electrostatic attraction between the oppositely charged polymers. Here, we report the first (to the best of our knowledge) complexation and coacervation of two positively charged polyelectrolytes, which provides a new paradigm for engineering strong, self-healing interactions between polyelectrolytes underwater and a new marine mussel-inspired underwater adhesion mechanism. Unlike the conventional complex coacervate, the like-charged coacervate is aggregated by strong short-range cation-π interactions by overcoming repulsive electrostatic interactions. The resultant phase of the like-charged coacervate comprises a thin and fragile polyelectrolyte framework and round and regular pores, implying a strong electrostatic correlation among the polyelectrolyte frameworks. The like-charged coacervate possesses a very low interfacial tension, which enables this highly positively charged coacervate to be applied to capture, carry, or encapsulate anionic biomolecules and particles with a broad range of applications.

  18. Interaction of Fluorocarbon Containing Hydrophobically Modified Polyelectrolyte with Nonionic Surfactants

    Institute of Scientific and Technical Information of China (English)

    GUO,Jin-Feng(郭金峰); ZHUANG,Dong-Qing(庄东青); ZHOU,Hui(周晖); ZHANG,Yun-Xiang(章云祥)

    2002-01-01

    The interaction of fluorocarbon containing hydrophobically modified polyelectrolyte (FMPAANa) with two kinds of nonionic surfactants (hydrogenated and fluorinated) in a semidilute (0.5 wt% ) aqueous solution had been studied by rheological measurements. Association behavior was found in both systems. The hydrophobic interaction of FMPAANa with fluorinated surfactant (FC171) is much stronger than that with hydrogenated surfactant (NP7.5) at low surfactant concentrations. The interaction is strengthened by surfactants being added for the density of active junctions increased. Whereas distinct phenomena for FC171 and NP7. 5 start to be found as the surfactants added over their respective certain concentration. The interaction of polyelectrolyte with fluorinated surfactant increases dramatical ly while that with hydrogenated surfactant decreases.

  19. Polyelectrolyte Coacervates Deposited as High Gas Barrier Thin Films.

    Science.gov (United States)

    Haile, Merid; Sarwar, Owais; Henderson, Robert; Smith, Ryan; Grunlan, Jaime C

    2017-01-01

    Multilayer coatings consisting of oppositely charged polyelectrolytes have proven to be extraordinarily effective oxygen barriers but require many processing steps to fabricate. In an effort to prepare high oxygen barrier thin films more quickly, a polyelectrolyte complex coacervate composed of polyethylenimine and polyacrylic acid is prepared. The coacervate fluid is applied as a thin film using a rod coating process. With humidity and thermal post-treatment, a 2 µm thin film reduces the oxygen transmission rate of 0.127 mm poly(ethylene terephthalate) by two orders of magnitude, rivalling conventional oxygen barrier technologies. These films are fabricated in ambient conditions using low-cost, water-based solutions, providing a tremendous opportunity for single-step deposition of polymeric high barrier thin films.

  20. Reversible Self-Assembly of Hydrophilic Inorganic Polyelectrolytes into Highly Conservative, Vesicle-like Structures

    Science.gov (United States)

    Kistler, Melissa; Bhatt, Anish; Liu, Guang; Liu, Tianbo

    2007-03-01

    The hydrophilic polyoxometalate (POM) macroanions are inorganic polyelectrolytes which offer a direct connection between simple ions and organic polyelectrolytes. POM solutions are perfect model systems for studying polyelectrolyte solutions because they are identical in size, shape, mass and charges, with easily tunable charge density. Many types of POM macroanions are highly soluble but undergo reversible self-assembly to form uniform, stable, soft, single-layer vesicle-like ``blackberry'' structures containing >1000 individual POMs in dilute solutions. The driving force of the blackberry formation is likely counterion-mediated attraction (like-charge attraction). The blackberry size can be accurately controlled by solvent quality, or the charge density on macroions. Many unexpected phenomena have been observed in these novel systems. Blackberry structures may be analogous to virus shell structures formed by capsid proteins. References: Nature, 2003, 426, 59; JACS, 2002, 124, 10942; 2003, 125, 312; 2004, 126, 16690; 2005, 127, 6942; 2006, 128, 10103.

  1. Polyelectrolyte multilayers prepared from water-soluble poly(alkoxythiophene) derivatives.

    Science.gov (United States)

    Lukkari, J; Salomäki, M; Viinikanoja, A; Aäritalo, T; Paukkunen, J; Kocharova, N; Kankare, J

    2001-06-27

    Electronically conducting polyanion and polycation based on poly(alkoxythiophene) derivatives, poly-3-(3'-thienyloxy)propanesulfonate (P3TOPS) and poly-3-(3'-thienyloxy)propyltriethylammonium (P3TOPA) have been synthesized. Both polymers are water-soluble and exhibit high conjugation length in solution and in the solid state. These polyelectrolytes were used to prepare conducting and electroactive polyelectrolyte multilayers by the sequential layer-by-layer adsorption technique. In aqueous solutions multilayers of P3TOPS with inactive polyelectrolytes (e.g., poly(diallyldimethylammonium chloride), PDADMA) displayed electrochemical and optical behavior similar to polythiophene films prepared in organic media. Their in-plane conductivity was low (ca. 1.6 x 10(-)(5) S cm(-)(1)). The conductivity could, however, be increased by a factor of ca. 40 in "all-thiophene" films, in which P3TOPA was substituted for the inactive polycation (PDADMA). The interpenetration of layers is of prime importance in films containing conducting components. The interpenetration of P3TOPS was studied by measuring the charge-transfer rate across an insulating polyelectrolyte multilayer between the substrate and the P3TOPS layer with modulated electroreflectance. The extent of interpenetration was 8-9 polyelectrolyte layers, the length scale (7-15 nm) depending on the nature of the insulating layer and, especially, on the ionic strength of the solution used for the adsorption of P3TOPS.

  2. Acrylamide-b-N-isopropylacrylamide block copolymers : Synthesis by atomic transfer radical polymerization in water and the effect of the hydrophilic-hydrophobic ratio on the solution properties

    NARCIS (Netherlands)

    Wever, Diego Armando Z.; Ramalho, Graham; Picchioni, Francesco; Broekhuis, Antonius Augustinus

    2014-01-01

    A series of block copolymers of acrylamide and N-isopropylacrylamide (NIPAM) characterized by different ratios between the length of the two blocks have been prepared through atomic transfer radical polymerization in water at room temperature. The solution properties of the block copolymers were cor

  3. Topology and Shape Control for Assemblies of Block Copolymer Blends in Solution

    KAUST Repository

    Moreno Chaparro, Nicolas

    2015-10-27

    We study binary blends of asymmetric diblock copolymers (AB/AC) in selective solvents with a mesoscale model. We investigate the morphological transitions induced by the concentration of the AC block copolymer and the difference in molecular weight between the AB and AC copolymers, when segments B and C exhibit hydrogen-bonding interactions. To the best of our knowledge, this is the first work modeling mixtures of block copolymers with large differences in molecular weight. The coassembly mechanism localizes the AC molecules at the interface of A and B domains and induces the swelling of the B-rich domains. The coil size of the large molecular weight block copolymer depends only on the concentration of the short block copolymer (AC or AB), regardless of the B–C interactions. However, the B–C interactions control the morphological transitions that occur in these blends.

  4. Adsorption of anionic polyelectrolytes to dioctadecyldimethylammonium bromide monolayers

    Science.gov (United States)

    Engelking, J.; Menzel, H.

    Monolayers of dioctadecyldimethylammonium bromide (DODA) at the air/water interface were used as model for charged surfaces to study the adsorption of anionic polyelectrolytes. After spreading on a pure water surface the monolayers were compressed and subsequently transferred onto a polyelectrolyte solution employing the Fromherz technique. The polyelectrolyte adsorption was monitored by recording the changes in surface pressure at constant area. For poly(styrene sulfonate) and carboxymethylcellulose the plot of the surface pressure as function of time gave curves which indicate a direct correlation between the adsorbed amount and surface pressure as well as a solely diffusion controlled process. In the case of rigid rod-like poly(p-phenylene sulfonate)s the situation is more complicated. Plotting the surface pressure as function of time results in a curve with sigmoidal shape, characterized by an induction period. The induction period can be explained by a domain formation, which can be treated like a crystallization process. Employing the Avrami expression developed for polymer crystallization, the change in the surface pressure upon adsorption of rigid rod-like poly(p-phenylene sulfonate)s can be described.

  5. Forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces.

    Science.gov (United States)

    Zhang, Ying; Wang, Lei; Wang, Xuejing; Qi, Guodong; Han, Xiaojun

    2013-07-01

    A novel method of forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces is introduced. Polyelectrolyte films were fabricated by the layer-by-layer technique on a silicon oxide surface modified with a 3-aminopropyltriethoxysilane (APTES) monolayer. The surface pK(a) value of the APTES monolayer was determined by cyclic voltammetry to be approximately 5.61, on the basis of which a pH value of 2.0 was chosen for layer-by-layer assembly. Micropatterned polyelectrolyte films were obtained by deep-UV (254 nm) photolysis though a mask. Absorbed fluorescent latex beads were used to visualize the patterned surfaces. Lipid bilayer arrays were fabricated on the micropatterned surfaces by immersing the patterned substrates into a solution containing egg phosphatidylcholine vesicles. Fluorescence recovery after photobleaching studies yielded a lateral diffusion coefficient for probe molecules of 1.31±0.17 μm(2) s(-1) in the bilayer region, and migration of the lipid NBD PE in bilayer lipid membrane arrays was observed in an electric field.

  6. Solubilization of trichloroethylene by polyelectrolyte/surfactant complexes

    Energy Technology Data Exchange (ETDEWEB)

    Uchiyama, Hirotaka; Christian, S.D.; Tucker, E.E.; Scamehorn, J.F. (Univ. of Oklahoma, Norman, OK (United States))

    1994-12-01

    An automated vapor pressure method is used to obtain solubilization isotherms for trichloroethylene (TCE) in polyelectrolyte/surfactant complexes throughout a wide range of solute activities at 20 and 25 C. The polyelectrolyte chosen is sodium poly(styrenesulfonate), PSS< and the surfactant is cetylpyridinium chloride or N-hexadecylpyridinium chloride, CPC. Data are fitted to the quadratic equation K = K[sub 0](1[minus][alpha]X + [beta]X[sup 2]), which correlates the solubilization equilibrium constant (K) with the mole fraction of TCE (X) in the micelles or complexes at each temperature. Activity coefficients are also obtained for TCE in the PSS/CPC complexes as a function of X. The general solubilization of TCE in PSS/CPC complexes resembles that of TCE in CPC micelles, as well as that of benzene or toluene in CPC micelles, suggesting that TCE solubilizes in ionic micelles both within the hydrocarbon micellar interior and near the micellar surface. The presence of the polyelectrolyte causes a small decrease in the ability of the cationic surfactant to solubilize TCE, while greatly reducing the concentration of the surfactant present in monomeric form. PSS/CPC complexes may be useful in colloid-enhanced ultrafiltration processes to purify organic-contaminated water.

  7. Linear Viscoelasticity and Swelling of Polyelectrolyte Complex Coacervates

    Science.gov (United States)

    Hamad, Fawzi; Colby, Ralph

    2012-02-01

    The addition of near equimolar amounts of poly(diallyldimethylammonium chloride) to poly(isobutylene-alt-maleate sodium), results in formation of a polyelectrolyte complex coacervate. Zeta-potential titrations conclude that these PE-complexes are nearly charge-neutral. Swelling and rheological properties are studied at different salt concentrations in the surrounding solution. The enhanced swelling observed at high salt concentration suggests the system behaves like a polyampholyte gel, and weaker swelling at very low salt concentrations implies polyelectrolyte gel behavior. Linear viscoelastic oscillatory shear measurements indicate that the coacervates are viscoelastic liquids and that increasing ionic strength of the medium weakens the electrostatic interactions between charged units, lowering the relaxation time and viscosity. We use the time-salt superposition idea recently proposed by Spruijt, et al., allowing us to construct master curves for these soft materials. Similar swelling properties observed when varying molecular weights. Rheological measurements reveal that PE-complexes with increasing molecular weight polyelectrolytes form a network with higher crosslink density, suggesting time-molecular weight superposition idea.

  8. Antibacterial polyelectrolyte-coated Mg alloys for biomedical applications

    Science.gov (United States)

    Seraz, Md. S.; Asmatulu, R.; Chen, Z.; Ceylan, M.; Mahapatro, A.; Yang, S. Y.

    2014-04-01

    This study deals with two biomedical subjects: corrosion rates of polyelectrolyte-coated magnesium (Mg) alloys, mainly used for biomedical purposes, and antibacterial properties of these alloys. Thin sheets of Mg alloys were coated with cationic polyelectrolyte chitosan (CHI) and anionic polyelectrolyte carboxymethyl cellulose (CMC) using a layer-by-layer coating method and then embedded with antibacterial agents under vacuum. Electrochemical impedance spectroscopy was employed to analyze these samples in order to detect their corrosion properties at different conditions. In the electrochemical analysis section, a corrosion rate of 72 mille inches per year was found in a salt solution for the sample coated with a 12 phosphonic acid self-assembled monolayer and 9 CHI/CMC multilayers. In the antibacterial tests, gentamicin was used to investigate the effects of the drug embedded with the coated surfaces against the Escherichia coli (E. coli) bacteria. Antibacterial studies were tested using the disk diffusion method. Based on the standard diameter of the zone of inhibition chart, the antibacterial diffusion from the surface strongly inhibited bacterial growth in the regions. The largest recorded diameter of the zone of inhibition was 50 mm for the pre-UV treated and gentamicin-loaded sample, which is more than three times the standard diameter.

  9. Self-Assembly of Amphiphilic Block Copolypeptoids with C 2 -C 5 Side Chains in Aqueous Solution

    KAUST Repository

    Fetsch, Corinna

    2014-12-22

    © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Nowadays, amphiphilic molecules play an important role in our life. In medical applications, amphiphilic block copolymers have attracted much attention as excipients in drug delivery systems. Here, the polymers are used as emulsifiers, micelles, or polymersomes with a hydrophilic corona block and a hydrophobic core or membrane. The aggregation behavior in aqueous solutions of a series of different amphiphilic block copolypeptoids comprising polysarcosine as a hydrophilic part is here reported. The formation of aggregates is investigated with 1H NMR spectroscopy and dynamic light scattering, and the determination of the critical micelle concentration (cmc) is performed using pyrene fluorescence spectroscopy. For the different block copolypeptoids cmc values ranging from 0.6 × 10-6 M to 0.1 × 10-3 M are found. The tendency to form micelles increases with increasing hydrophobicity at the nitrogen side chain in the hydrophobic moiety. Furthermore, in the case of the same hydrophobic side chain, a decreasing hydrophilic/lipophilic balance leads to the formation of larger aggregates. The aggregates formed in the buffer are able to solubilize the hydrophobic model compounds Reichardt\\'s dye and pyrene, and exhibit versatile microenvironments. Final investigations about the cytotoxicity reveal that the block copolypeptoids are well tolerated by mammalian cells up to high concentrations.

  10. Systematic modification of the rheological properties of colloidal suspensions with polyelectrolyte multilayers.

    Science.gov (United States)

    Hess, Andreas; Pretzl, Melanie; Heymann, Lutz; Fery, Andreas; Aksel, Nuri

    2011-09-01

    Tailoring rheological properties of colloidal suspensions with the adsorption of polyelectrolyte multilayers (PEMs) is based on the idea of controlling macroscopic mechanical properties by modifying the particle surface in a reproducible and well-understood manner. With layer-by-layer self-assembly, monodisperse polystyrene particles are coated with up to ten layers of the oppositely charged strong polyelectrolytes: poly(diallyl dimethyl ammonium chloride) and poly(styrene sulfonate). The conformation of the adsorbed polyelectrolyte is controlled by the ionic strength of the used aqueous polyelectrolyte solution. For 1M NaCl solution, a brushlike adsorption of the polyelectrolyte is expected. The ability of PEMs to serve on a nanoscale level as surface modifiers and influence macroscopic rheological properties like viscoelasticity, yield stress, and shear banding is discussed. The mechanical behavior of these suspensions is qualitatively described by the theory of Derjaguin-Landau-Verwey-Overbeek with short-range repulsion and long-range attraction. A scaling rule is proposed which distinguishes between the precusor and the multilayer regime.

  11. MOLECULAR DYNAMIC SIMULATION OF PEPTIDE POLYELECTROLYTES

    Directory of Open Access Journals (Sweden)

    I. M. Neelov

    2014-07-01

    Full Text Available The paper deals with investigation of the conformational properties of some charged homopolypeptides in dilute aqueous solutions by computer simulation. A method of molecular dynamics for the full-atomic models of polyaspartic acid and polylysine with explicit account of water and counter-ions is used for this purpose. For systems containing these polypeptides we calculated time trajectories and the size, shape, distribution functions and time correlation functions of inertia radius and the distances between the ends of peptide chains. We have also calculated the solvatation characteristics of considered polyelectrolytes. We have found out that polyaspartic acid in dilute aqueous solution has more compact structure and more spherical shape than polylysine. We have shown that these differences are due to different interaction between the polypeptides and water molecules (in particular, the quality and quantity of hydrogen bonds formed by these peptides with water, and the difference in an amount of ion pairs formed by the charged groups of the peptides and counter-ions. The obtained results should be taken into account for elaboration of new products based on the investigated peptides and their usage in various industrial and biomedical applications.

  12. Macroion induced dehydration of weak polyelectrolyte brushes

    Science.gov (United States)

    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.

  13. Functionalized conjugated polyelectrolytes design and biomedical applications

    CERN Document Server

    Wang, Shu

    2014-01-01

    Functionalized Conjugated Polyelectrolytes presents a comprehensive review of these polyelectrolytes and their biomedical applications. Basic aspects like molecular design and optoelectronic properties are covered in the first chapter. Emphasis is placed on the various applications including sensing (chemical and biological), disease diagnosis, cell imaging, drug/gene delivery and disease treatment. This book explores a multi-disciplinary topic of interest to researchers working in the fields of chemistry, materials, biology and medicine. It also offers an integrated perspective on both basic research and application issues. Functionalized conjugated polyelectrolyte materials, which have already drawn considerable interest, will become a major new direction for biomedicine development.

  14. Shear devices for in situ structural studies of block copolymer melts and solutions

    DEFF Research Database (Denmark)

    Mortensen, K.; Almdal, K.; Bates, F.S.

    1995-01-01

    Structural studies of soft material while exposed in situ to stretch or shear provide a new experimental technique which gives important insight into polymer dynamics. Such devices can be used for making single-domain block-copolymer and colloidal mesophases, and to study various growth mechanisms...

  15. Characterization of solution structure and its importance in thin film ordering of conjugated block copolymers for organic semiconductor devices

    Science.gov (United States)

    Brady, Michael; Ku, Sung-Yu; Cochran, Justin; Wang, Cheng; Hawker, Craig; Kramer, Edward; Chabinyc, Michael

    2014-03-01

    Fully conjugated diblock copolymers (CBCPs) form intriguing materials alternatives to polymer-small molecule blends for their control of mesoscopic order in low-cost organic semiconductor devices. In both bulk heterojunction (BHJ) photovoltaics, consisting of an interpenetrating network with high donor-acceptor interfacial area, and ambipolar transistors, the transport of charge carriers through continuous p- and n-type paths in thin films is a controlling factor in device performance. AFM, GIWAXS, NEXAFS spectroscopy, and RSoXS are used to probe the structure of films of CBCPs with a p-type P3HT block and an n-type DPP block. Thermal annealing in the P3HT melt after casting creates ordered domains with ~ 50 nm in-plane lamellar spacings, as confirmed with GISAXS and RSoXS. GIWAXS diffraction from the (h00) alkyl-stacking and (010) pi-stacking planes shows primarily edge-on orientation for crystals of both P3HT and DPP blocks. In addition, temperature-dependent solution SAXS and UV-Vis spectroscopy are used to probe the size and conformation of casting solution aggregates. Fibrillar DPP aggregates direct the crystallization of P3HT- b-DPP following film casting and enable the formation of wormlike domains after annealing and thus ideal morphologies for transport in organic devices.

  16. Anionic Polyelectrolyte-Cationic Surfactant Interactions in Aqueous Solutions and Foam Films Stability Interactions entre polyélectrolytes anioniques et tensioactifs cationiques en solutions aqueuses et stabilité des films de mousses

    Directory of Open Access Journals (Sweden)

    Langevin D.

    2006-12-01

    Full Text Available The objective of this work is to study polymer/surfactant interactions in aqueous solution and at the air/water interface. These interations are involved in many physicochemical phenomena, such as colloidal stabilization and wettability which are of major importance in oil application as for exemple drilling muds. More precisely, we have attempted to characterize interactions between a non surface active anionic copolymer (acrylamide/acrylamide sulfonate and an oppositely charged cationic surfactant (C12 TAB. Our results show a synergestic surface tension lowering (coadsorption at extremely low surfactant concentrations (10 to the power of (-3 to 10 to the power of (-1 CMC. At higher concentrations, namely above the so called Critical Aggregation Concentration (CAC, polymer-surfactant complexes form in the bulk and the macromolecules precipitate out of the solution. Foam films made from these mixed solutions are stable while C12TAB films are unstable. Disjoining pressure measurements on mixed films with surfactant concentration two orders of magnitude below the CAC show the existence of long range repulsive forces and a discrete film thickness transition. At the CAC, we obtain mixed films with gel-like networks that are strongly affected by the film thinning rate. L'objectif de cette étude est d'étudier les interactions polymère/tensioactif en solution aqueuse et à l'interface eau/air. Ces interactions interviennent dans de nombreux phénomènes physico-chimiques tels que la stabilisation de suspensions colloïdales et la mouillabilité qui sont d'une importance majeure dans les applications pétrolières comme, par exemple, les boues de forage. Plus précisément, nous avons essayé de caractériser les interactions entre un copolymère anionique n'ayant pas d'activité de surface (acrylamide/acrylamide sulfoné avec un tensioactif de charge opposée cationique (C12TAB. Nos résultats montrent une diminution synergique de la tension

  17. Responsive polyelectrolyte hydrogels and soft matter micromanipulation

    NARCIS (Netherlands)

    Glazer, P.J.

    2013-01-01

    This dissertation describes experimental studies on the mechanisms underlying the dynamic response of polyelectrolyte hydrogels when submitted to an external electric potential. In addition, we explore the possibilities of miniaturization and manipulation of responsive gels and other soft matter sys

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

    Science.gov (United States)

    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

  19. The effect of temperature and pressure on the oxygen reduction reactions in polyelectrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

    1997-12-31

    The effect of temperature and pressure on the oxygen reduction reaction in polyelectrolyte membranes was described. Polyelectrolytes chosen for the experiment differed in composition, weight and flexibility of the polymer chains. The study was conducted in a solid state electrochemical cell at temperatures between 30 and 95 degrees C and in the pressure range of 1 to 5 atm. The solubility of oxygen in these membranes was found to follow Henry`s Law, while the diffusion coefficient decreased with pressure. The effect of temperature on the solubility of oxygen and the diffusion coefficient of oxygen in the membranes was similar to that observed in solution electrolytes. 2 refs., 3 figs.

  20. Self-assembly behavior of well-defined polymethylene-block-poly(ethylene glycol) copolymers in aqueous solution

    KAUST Repository

    Alkayal, Nazeeha

    2016-09-22

    A series of well-defined amphiphilic polymethylene-b-poly(ethylene glycol) (PM-b-PEG) diblock copolymers, with different hydrophobic chain length, were synthesized by combining Diels-Alder reaction with polyhomologation. The successful synthetic procedure was confirmed by size-exclusion chromatography (SEC) and 1H NMR spectroscopy. These block copolymers self-assembled into spherical micelles in aqueous solutions and exhibit low critical micelle concentration (CMC) of 2–4 mg/mL, as determined by fluorescence spectroscopy using pyrene as a probe. Measurements of the micelle hydrodynamic diameters, performed by dynamic light scattering (DLS), cryo-transmission electron microscopy (cryo-TEM) and atomic force microscopy (AFM), revealed a direct dependence of the micelle size from the polymethylene block length.

  1. A Closed-form Solution to Finite Bending of a Compressible Elastic-perfectly Plastic Rectangular Block

    Directory of Open Access Journals (Sweden)

    H. Xiao

    2003-01-01

    Full Text Available The self-consistent Eulerian rate-type elastoplastic model based on the logarithmic rate is used to study finite bending of a compressible elastic-perfectly plastic rectangular block. It is found that an explicit closed-form solution for this typical inhomogeneous finite deformation , mode may be available in a general case of compressible deformation with a stretch normal to the bending plane, where the maximum circumferential stretch at the outer surface serves as an Independent parameter. Expressions are given for the bending angle, the bending moment, the the outer and the inner radii, and the radii of the two moving elastic-plastic interfaces, etc. The exact stress distribution on any circumferential cross-section of the deformed block is accordingly determined.

  2. Polyelectrolyte properties of filamentous biopolymers and their consequences in biological fluids.

    Science.gov (United States)

    Janmey, Paul A; Slochower, David R; Wang, Yu-Hsiu; Wen, Qi; Cēbers, Andrejs

    2014-03-14

    Anionic polyelectrolyte filaments are common in biological cells. DNA, RNA, the cytoskeletal filaments F-actin, microtubules, and intermediate filaments, and polysaccharides such as hyaluronan that form the pericellular matrix all have large net negative charge densities distributed over their surfaces. Several filamentous viruses with diameters and stiffnesses similar to those of cytoskeletal polymers also have similar negative charge densities. Extracellular protein filaments such collagen, fibrin and elastin, in contrast, have notably smaller charge densities and do not behave as highly charged polyelectrolytes in solution. This review summarizes data that demonstrate generic counterion-mediated effects on four structurally unrelated biopolymers of similar charge density: F-actin, vimentin, Pf1 virus, and DNA, and explores the possible biological and pathophysiological consequences of the polyelectrolyte properties of biological filaments.

  3. [Mechanical characteristics of synthetic polyelectrolyte gel as a physical model of the cytoskeleton].

    Science.gov (United States)

    Shkliar, T F; Toropova, O A; Safronov, A P; Pollack, G H; Bliakhman, F A

    2011-01-01

    A physical model of the cytoskeleton based on synthetic polyelectrolyte hydrogel of polymethacrylic acid has been proposed. From the physicochemical point of view, the structures of polyelectrolyte gel and the cytoskeleton show a high degree of similarity. It was shown that polyelectrolyte gel can shorten and produce mechanical stress in response to changes in the composition of the surrounding solution. The mechanical properties of the model gel were evaluated: Young modulus (2-6 kPa), stress relaxation time (0.1-1 s), and apparent viscosity (0.3-3 kPa x s). The viscoelastic properties of the gel depend on the degree of its swelling. It has been demonstrated that the mechanical properties of gels of polymethacrylic acid are close to those of biological objects.

  4. Novel chemiluminescent Western blot blocking and antibody incubation solution for enhanced antibody-antigen interaction and increased specificity.

    Science.gov (United States)

    Schwartz, Kimberly; Bochkariov, Dmitry

    2017-07-13

    Western blotting is a ubiquitous tool used in protein and molecular biology research, providing information about the presence, size, relative abundance, and state of a protein in a mixture. First, the proteins in a sample are separated by size using SDS-PAGE then transferred onto a membrane for detection with a set of primary and secondary antibodies. High-quality Western data requires high signal-to-noise ratios, which depend upon reduction of nonspecific antibody interactions. Blocking is a critical step in the Western blot method as it prevents the antibodies from binding nonspecifically to the membrane and irrelevant proteins. A solution of nonfat dry milk (NFDM) in physiological buffer is commonly used for this purpose, but does not perform well with every type of antibody and is not optimal for low-abundance proteins. We present a novel blocking solution for chemiluminescent Western blots, AdvanBlock™-chemi, which outperforms NFDM in experiments with 20 unique antibodies by increasing signal-to-noise ratios and minimizing nonspecific binding. This solution enhances protein detection by Western blot and provides consistent results for detection of low abundant and modified proteins. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Micelles and gels of oxyethylene-oxybutylene diblock copolymers in aqueous solution: The effect of oxyethylene-block length

    DEFF Research Database (Denmark)

    Derici, L.; Ledger, S.; Mai, S.M.

    1999-01-01

    Block copolymer E(90)B(10) (E = oxyethylene, B = oxybutylene) was synthesised and characterised by gel permeation chromatography and (13)C NMR spectroscopy. Dynamic light scattering (DLS) and static light scattering (SLS) were used to characterise the micelles in solution (both in water and in aq......Block copolymer E(90)B(10) (E = oxyethylene, B = oxybutylene) was synthesised and characterised by gel permeation chromatography and (13)C NMR spectroscopy. Dynamic light scattering (DLS) and static light scattering (SLS) were used to characterise the micelles in solution (both in water.......e., the association number, the hard-sphere radius, the micelle volume fraction and the corresponding expansion factors. A comparison of the appropriate quantities showed good agreement between the two techniques. SANS gave additional information e.g., volume fraction profiles for the micelles and volume fraction...... of water in the micelle core. Moderately concentrated solutions of copolymer E(90)B(10) were studied in the gel state by small-angle X-ray scattering (SAXS) in tandem with rheology (oscillatory shear). Values for the dynamic elastic modulus (G') of the gels significantly exceeded 10(4) Pa across the range...

  6. Polyelectrolyte Building Blocks for Nanotechnology: Atomic Force Microscopy Investigations of Polyelectrolyte-Lipid Interactions, Polyelectrolyte Brushes and Viral Cages

    OpenAIRE

    2013-01-01

    The work presented here has a multidisciplinary character, having as a common factor the characterization of self-assembled nanostructures through force spectroscopy. Exploring AFM as a tool for characterizing self-assembly and interaction forces in soft matter nanostructures, three different Bio and nonbiological systems where investigated, all of them share the common characteristic of being soft matter molecular structures at the nanoscale. The studied systems in question are: a) Polyelect...

  7. Complexation behavior of oppositely charged polyelectrolytes: Effect of charge distribution

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Mingtian; Li, Baohui, E-mail: dliang@pku.edu.cn, E-mail: baohui@nankai.edu.cn [School of Physics and Key Laboratory of Functional Polymer Materials of Ministry of Education, Nankai University, Tianjin 300071 (China); Zhou, Jihan; Su, Cuicui; Niu, Lin; Liang, Dehai, E-mail: dliang@pku.edu.cn, E-mail: baohui@nankai.edu.cn [Beijing National Laboratory for Molecular Sciences and the Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

    2015-05-28

    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 not 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

  8. Block copolymer micelle coronas as quasi-two-dimensional dilute or semidilute polymer solutions

    DEFF Research Database (Denmark)

    Svaneborg, C.; Pedersen, J.S.

    2001-01-01

    Chain-chain interactions in a corona of polymers tethered to a spherical core under good solvent conditions are studied using Monte Carlo simulations. The total scattering function of the corona as well as different partial contributions are sampled. By combining the different contributions...... in a self-consistent approach, it is demonstrated that the corona can be regarded as a quasi-two-dimensional polymer solution, with a concentration dependence analogous to that of an ordinary polymer solution. Scattering due to the corona profile and density fluctuation correlations are separated...

  9. Investigation on the interaction of Safranin T with anionic polyelectrolytes by spectrophotometric method.

    Science.gov (United States)

    Fradj, Anouar Ben; Lafi, Ridha; Hamouda, Sofiane Ben; Gzara, Lassaad; Hamzaoui, Ahmed Hichem; Hafiane, Amor

    2014-10-15

    Understanding the role played by chemical additives such as NaCl salt, acid and Cetylpyridinium Chloride (CPC) surfactant on the interaction between dye and polyelectrolyte contributes to optimization of processes using polyelectrolytes in the removal of dye from aqueous solution. Herein we focus in the interaction between Safranin T, a cationic dye, with two anionic polyelectrolytes, poly(ammonium acrylate) and poly(acrylic acid) using spectrophotometric method and conductivity measurement. In aqueous solution, each of anionic polyelectrolytes forms a complex with the dye and induces a metachromasy indicated by the blue shift of the absorbance of the dye. The stoichiometry of complexes evaluated by the molar ratio method are 1:1 for Safranin T poly(ammonium acrylate) and 2:1 in the case of Safranin T poly(acrylic acid). The effect of additives on the stability of complexes has been studied by varying concentrations of the salt and the surfactant and pH of the solution. The thermodynamic parameters of interaction ΔG, ΔH and ΔS at different temperatures were evaluated to determine the stability constant of the complexes.

  10. Characterization of polyelectrolyte behavior of the polysaccharides chitosan, heparin, and hyaluronan, by light scattering and viscometry.

    Science.gov (United States)

    Boddohi, Soheil; Yonemura, Susan; Kipper, Matt

    2008-03-01

    This study on the polyelectrolyte behavior of polysaccharides in solution is motivated by our recent work in development of nanostructured polysaccharide-based surface coatings. Chitosan behaves as a weak polycation, and hyaluronan behaves as a weak polyanion, while heparin behaves as a strong polyanion. The ability to control the conformation of these polysaccharides in solution, by changing the solution ionic strength and pH may offer the opportunity to further tune the nanoscale features of polysaccharide-based surface coatings assembled from solution. In the work reported here, the solution conformation of these polymers is determined from gel permeation chromatography coupled to differential refractive index, light scattering, and viscometry detection. These results are related to the nanostructure of chitosan-heparin and chitosan-hyaluronan surface coatings based on polyelectrolyte multilayers.

  11. Complex coacervation of supercharged proteins with polyelectrolytes.

    Science.gov (United States)

    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.

  12. Block-pulse functions approach to numerical solution of Abel’s integral equation

    Directory of Open Access Journals (Sweden)

    Monireh Nosrati Sahlan

    2015-12-01

    Full Text Available This study aims to present a computational method for solving Abel’s integral equation of the second kind. The introduced method is based on the use of Block-pulse functions (BPFs via collocation method. Abel’s integral equations as singular Volterra integral equations are hard and heavy in computation, but because of the properties of BPFs, as is reported in examples, this method is more efficient and more accurate than some other methods for solving this class of integral equations. On the other hand, the benefit of this method is low cost of computing operations. The applied method transforms the singular integral equation into triangular linear algebraic system that can be solved easily. An error analysis is worked out and applications are demonstrated through illustrative examples.

  13. Formation and degradation of layer-by-layer-assembled polyelectrolyte polyrotaxane capsules.

    Science.gov (United States)

    Dam, Henk H; Caruso, Frank

    2013-06-18

    We report the preparation of degradable capsules via layer-by-layer assembly using polyelectrolyte (PE) polyrotaxanes (PRXs). The PRX capsules were prepared by the sequential deposition of PRXs onto silica particles followed by the dissolution of the silica cores. The colloidal stability of the PRX capsules that are formed depends on the salt/buffer solution used in the assembly process. Various salt/buffer combinations were examined to avoid aggregation of the core-shell particles during PRX assembly and core dissolution. Using appropriate assembly conditions, we prepared colloidally stable, robust capsules. PRX capsules consisting of eight layers of PE PRXs had a wall thickness of ~15 nm. The degradation of the PRX capsules was demonstrated through the disassembly of the PE PRXs using glutathione, which cleaves the disulfide bonds linking the end-capping groups of the PE PRXs. Given the supramolecular noncovalent structure of PRXs and their adjustable properties, it is expected that PRXs will be used as building blocks for assembling advanced capsules with unique and tailored properties.

  14. Compacted graphite iron-A material solution for modern diesel engine cylinder blocks and heads

    Institute of Scientific and Technical Information of China (English)

    Steve Dawson; SinterCast; Sweden

    2009-01-01

    The demands for improved fuel economy,performance and emissions continue to pose challenges for engine designers and the materials they choose. This is particularly true for modern diesel engines,where the primary path to achieving improved engine performance and emissions is to increase the Peak Firing Pressure in the combustion chamber. The resulting increase in thermal and mechanical loading has required a change from conventional grey cast iron to Compacted Graphite Iron (CGI) in order to satisfy durability requirements without increasing the size or the weight of the engines. With at least 75% higher tensile strength,45% higher stiffness and approximately double the fatigue strength of conventional grey cast iron,CGI satisfies durability requirements and also provides the dimensional stability required to meet emissions legislation throughout the life of the engine.Currently,there are no CGI diesel engines running on the roads in North America. This is set to change considerably as new commercial vehicle and pick-up SUV diesel engines are launched with CGI cylinder blocks in 2008 and 2009. These initial programs will provide over 2 million CGI diesel engines when ramped to mature volume,potentially accounting for 10%-15% of the North American passenger vehicle fleet within the next four years.

  15. Compacted graphite iron – A material solution for modern diesel engine cylinder blocks and heads

    Directory of Open Access Journals (Sweden)

    Dr. Steve Dawson

    2009-08-01

    Full Text Available The demands for improved fuel economy, performance and emissions continue to pose challenges for engine designers and the materials they choose. This is particularly true for modern diesel engines, where the primary path to achieving improved engine performance and emissions is to increase the Peak Firing Pressure in the combustion chamber. The resulting increase in thermal and mechanical loading has required a change from conventional grey cast iron to Compacted Graphite Iron (CGI in order to satisfy durability requirements without increasing the size or the weight of the engines. With at least 75% higher tensile strength, 45% higher stiffness and approximately double the fatigue strength of conventional grey cast iron, CGI satisfi es durability requirements and also provides the dimensional stability required to meet emissions legislation throughout the life of the engine. Currently, there are no CGI diesel engines running on the roads in North America. This is set to change considerably as new commercial vehicle and pick-up SUV diesel engines are launched with CGI cylinder blocks in 2008 and 2009. These initial programs will provide over 2 million CGI diesel engines when ramped to mature volume, potentially accounting for 10%–15% of the North American passenger vehicle fleet within the next four years.

  16. Energy conversion in polyelectrolyte hydrogels

    Science.gov (United States)

    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).

  17. Synthesis and Solution Properties of Double Hydrophilic Poly(ethylene oxide)-block-poly(2-ethyl-2-oxazoline) (PEO-b-PEtOx) Star Block Copolymers

    National Research Council Canada - National Science Library

    Tobias Rudolph; Sarah Crotty; Moritz von der Lühe; David Pretzel; Ulrich S Schubert; Felix H Schacher

    2013-01-01

      We demonstrate the synthesis of star-shaped poly(ethylene oxide)-block-poly(2-ethyl-2-oxazoline) [PEOm-b-PEtOxn]x block copolymers with eight arms using two different approaches, either the "arm-first" or the "core-first" strategy...

  18. Cationic β-cyclodextrin polymer applied to a dual cyclodextrin polyelectrolyte multilayer system.

    Science.gov (United States)

    Junthip, Jatupol; Tabary, Nicolas; Leclercq, Laurent; Martel, Bernard

    2015-08-01

    A polyelectrolyte multilayer film (PEM) based on cationic and anionic β-cyclodextrin polyelectrolytes was coated onto a textile substrate for future drug delivery purposes. We firstly synthesized a novel cationic β-cyclodextrin polymer (polyEPG-CD) by crosslinking β-cyclodextrin (βCD) with epichlorohydrin (EP) under basic conditions, in the presence of glycidyltrimetrylammonium chloride (GTMAC) as cationizing group. The influence of preparation conditions has been investigated in order to preferably obtain a water soluble fraction whose charge density and molecular weights were optimal for the layer-by-layer (LbL) deposition process. The different cationic cyclodextrin polymers obtained were characterized by FTIR, NMR, colloidal titration, conductimetry, thermogravimetric analysis and size exclusion chromatography. Besides, the counterpart polyelectrolyte was a β-cyclodextrin polymer crosslinked with citric acid, polyCTR-CD, whose synthesis and characterization have been previously reported. Finally we realized the Layer by Layer (LbL) build-up of the PEM coating onto the textile support, using the dip coating method, by alternatively soaking it in cationic polyEPG-CD and anionic polyCTR-CD solutions. This multilayer self-assembly was monitored by SEM, gravimetry and OWLS in function of both polyelectrolytes concentrations and ratios. Solutions parameters such as pH, ionic strenght were also discussed.

  19. Regenerable Polyelectrolyte Membrane for Ultimate Fouling Control in Forward Osmosis.

    Science.gov (United States)

    Kang, Yan; Zheng, Sunxiang; Finnerty, Casey; Lee, Michael J; Mi, Baoxia

    2017-03-21

    This study demonstrated the feasibility of using regenerable polyelectrolyte membranes to ultimately control the irreversible membrane fouling in a forward osmosis (FO) process. The regenerable membrane was fabricated by assembling multiple polyethylenimine (PEI) and poly(acrylic acid) (PAA) bilayers on a polydopamine-functionalized polysulfone support. The resulting membrane exhibited higher water flux and lower solute flux in FO mode (with the active layer facing feed solution) than in PRO mode (with the active layer facing draw solution) using trisodium citrate as draw solute, most likely due to the unique swelling behavior of the polyelectrolyte membrane. Membrane regeneration was conducted by first dissembling the existing PEI-PAA bilayers using strong acid and then reassembling fresh PEI-PAA bilayers on the membrane support. It was found that, after the acid treatment, the first covalently bonded PEI layer and some realigned PAA remained on the membrane support, acting as a beneficial barrier that prevented the acid-foulant mixture from penetrating into the porous support during acid treatment. The water and solute flux of the regenerated membrane was very similar to that of the original membrane regardless of alginate fouling, suggesting an ultimate solution to eliminating the irreversible membrane fouling in an FO process. With a procedure similar to the typical membrane cleaning protocol, in situ membrane regeneration is not expected to noticeably increase the membrane operational burden but can satisfactorily avoid the expensive replacement of the entire membrane module after irreversible fouling, thereby hopefully reducing the overall cost of the membrane-based water-treatment system.

  20. Spin-Coated Polyelectrolyte Coacervate Films.

    Science.gov (United States)

    Kelly, Kristopher D; Schlenoff, Joseph B

    2015-07-01

    Thin films of complexes made from oppositely charged polyelectrolytes have applications as supported membranes for separations, cell growth substrates, anticorrosion coatings, biocompatible coatings, and drug release media, among others. The relatively recent technique of layer-by-layer assembly reliably yields conformal coatings on substrates but is impractically slow for films with thickness greater than about 1 μm, even when accelerated many fold by spraying and/or spin assembly. In the present work, thin, uniform, smooth films of a polyelectrolyte complex (PEC) are rapidly made by spin-coating a polyelectrolyte coacervate, a strongly hydrated viscoelastic liquidlike form of PEC, on a substrate. While the apparatus used to deposit the PEC film is conventional, the behavior of the coacervate, especially the response to salt concentration, is highly nontraditional. After glassification by immersion in water, spun-on films may be released from their substrates to yield free-standing membranes of thickness in the micrometer range.

  1. Waste-moulding dusts modified with polyelectrolytes

    Directory of Open Access Journals (Sweden)

    A. Baliński

    2010-04-01

    Full Text Available In the article described problems of the influence of advanced oxidizing process, the supersonic tooling of waste - moulding dusts and their modification with polyelectrolytes, on the technological proprieties of the moulding sands prepared with their participation.Physicochemical characterization of the used polyelectrolytes PSS (poli 4-styreno sodium sulfonate and PEI (poli etyleno imine, in theaspect of their modificatory influences on the waste - moulding dust, was described. Defined the influence of adsorption proprieties ofthe polyelectrolyte PEI on the surface of small parts of the waste - dust, on technological proprieties of the sandmix. Ascertained theprofitable influence of this electrolyte on mechanical proprieties of the moulding sands, that is to say the increase in value of thecompression strength (about 10% and tensile strenght (about 13%, comparatively to analogous proprieties of the moulding sandsprepared with the participation of the not modified waste- dust.

  2. Responsive Hydrogels from Associative Block Copolymers: Physical Gelling through Polyion Complexation

    Directory of Open Access Journals (Sweden)

    Christine M. Papadakis

    2017-01-01

    Full Text Available The present review article highlights a specific class of responsive polymer-based hydrogels which are formed through association of oppositely charged polyion segments. The underpinning temporary three-dimensional network is constituted of hydrophilic chains (either ionic or neutral physically crosslinked by ion pair formation arising from intermolecular polyionic complexation of oppositely charged repeating units (polyacid/polybase ionic interactions. Two types of hydrogels are presented: (i hydrogels formed by triblock copolymers bearing oppositely charged blocks (block copolyampholytes, forming self-assembled networks; and (ii hydrogels formed by co-assembly of oppositely charged polyelectrolyte segments belonging to different macromolecules (either block copolymers or homopolyelectrolytes. Due to the weak nature of the involved polyions, these hydrogels respond to pH and are sensitive to the presence of salts. Discussing and evaluating their solution, rheological and structural properties in dependence on pH and ionic strength, it comes out that the hydrogel properties are tunable towards potential applications.

  3. Adsorption of weak polyelectrolytes on charged nanoparticles. Impact of salt valency, pH, and nanoparticle charge density. Monte Carlo simulations.

    Science.gov (United States)

    Carnal, Fabrice; Stoll, Serge

    2011-10-27

    Complex formation between a weak flexible polyelectrolyte chain and one positively charged nanoparticle in presence of explicit counterions and salt particles is investigated using Monte Carlo simulations. The influence of parameters such as the nanoparticle surface charge density, salt valency, and solution property such as the pH on the chain protonation/deprotonation process and monomer adsorption at the nanoparticle surface are systematically investigated. It is shown that the nanoparticle presence significantly modifies chain acid/base and polyelectrolyte conformational properties. The importance of the attractive electrostatic interactions between the chain and the nanoparticle clearly promotes the chain deprotonation leading, at high pH and nanoparticle charge density, to fully wrapped polyelectrolyte at the nanoparticle surface. When the nanoparticle bare charge is overcompensated by the polyelectrolyte charges, counterions and salt particles condense at the surface of the polyelectrolyte-nanoparticle complex to compensate for the excess of charges providing from the adsorbed polyelectrolyte chain. It is also shown that the complex formation is significantly affected by the salt valency. Indeed, with the presence of trivalent salt cations, competition is observed between the nanoparticle and the trivalent cations. As a result, the amount of adsorbed monomers is less important than in the monovalent and divalent case and chain conformations are different due to the collapse of polyelectrolyte segments around trivalent cations out of the nanoparticle adsorption layer.

  4. Solution processable colloidal nanoplates as building blocks for high-performance electronic thin films on flexible substrates.

    Science.gov (United States)

    Lin, Zhaoyang; Chen, Yu; Yin, Anxiang; He, Qiyuan; Huang, Xiaoqing; Xu, Yuxi; Liu, Yuan; Zhong, Xing; Huang, Yu; Duan, Xiangfeng

    2014-11-12

    Low-temperature solution-processed electronic materials on plastic substrates are of considerable interest for flexible electronics. Solution dispersible inorganic nanostructures (e.g., zero-dimensional (0D) quantum dots or one-dimensional (1D) nanowires) have emerged as interesting ink materials for low-temperature solution processing of electronic thin films on flexible substrates, but usually with limited performance due to the large number of grain boundaries (0D) or incomplete surface coverage (1D). Here, we report two-dimensional (2D) colloidal nanoplates of layered materials as a new ink material for solution assembly of high-performance electronic thin films. The 2D colloidal nanoplates exhibit few dangling bonds and represent an ideal geometry for the assembly of highly uniform continuous thin films with greatly reduced grain boundaries dictated by large-area conformal plane-plane contact with atomically flat/clean interfaces. It can therefore promise efficient charge transport across neighboring nanoplates and throughout the entire thin film to enable unprecedented electronic performance. We show that Bi2Se3 and Bi2Te3 nanoplates can be synthesized with well-controlled thickness (6-15 nm) and lateral dimension (0.5-3 μm) and can be used for the assembly of highly uniform continuous thin films with a full surface coverage and an excellent room temperature carrier mobility >100 cm(2)·V(-1)·s(-1), approaching that of chemical vapor deposition grown materials. Our study demonstrates a general strategy to using 2D nanoplates as a unique building block for the construction of high-performance electronic thin films on plastic substrates for future flexible electronics and optoelectronics.

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

    Directory of Open Access Journals (Sweden)

    Lim CM

    2016-02-01

    Full Text Available Chaemin Lim,1,* Yu Seok Youn,2,* Kyung Soo Lee,1 Ngoc Ha Hoang,1 Taehoon Sim,1 Eun Seong Lee,3 Kyung Taek Oh1 1Department of Pharmaceutical Sciences, College of Pharmacy, Chung-Ang University, Seoul, 2Department of Pharmaceutical Sciences, School of Pharmacy, Sungkyunkwan University, Suwon, 3Division of Biotechnology, The Catholic University of Korea, Gyeonggi-do, South Korea *These authors contributed equally to this work Abstract: 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. Keywords: polyelectrolyte ionomer complex, PEG–PLA–PEI, nanomedicine, pH-sensitive, animal imaging

  6. Study of the effects of the reaction conditions on the modification of clays with polyelectrolytes and silanes.

    Science.gov (United States)

    de la Orden, M U; Arranz, J; Lorenzo, V; Pérez, E; Martínez Urreaga, J

    2010-02-01

    New organically modified clays have been obtained from sodium montmorillonite, using either a cationic polyelectrolyte (polyethylenimine) or a novel homemade bisphenol-A silane as modifiers. The modification processes have been carried out in different reaction media, in order to study the effects on the properties of the modified clays of several reaction parameters, such as the pH of the polyethylenimine solution or the nature of the solvent used in the silanization. The obtained clays were characterized using X-ray diffraction, thermogravimetric analysis, and FTIR spectroscopy. Clays modified with polyelectrolyte or silane show significant increases in the basal spacing. The properties of polyelectrolyte-modified clays depend on the pH of the treating solution. The increase in the basal spacing of polyelectrolyte-modified clays varies only slightly with the pH; however, this reaction parameter clearly determines the total amount of polyelectrolyte introduced in the clay. The properties and applications of silane-modified clays are strongly dependent on the presence of water in the reaction media used for the silanization. These results have been explained by considering that the reaction conditions determine the nature and the amount of material intercalated into the clay.

  7. PROPERTIES OF DOUBLE-STRANDED DNA AS A POLYELECTROLYTE.

    Science.gov (United States)

    OHNISHI, T

    1963-11-01

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

  8. Fabrication of ultrathin polyelectrolyte fibers and their controlled release properties.

    Science.gov (United States)

    Chunder, Anindarupa; Sarkar, Sourangsu; Yu, Yingbo; Zhai, Lei

    2007-08-01

    Ultrathin fibers comprising 2-weak polyelectrolytes, poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) were fabricated using the electrospinning technique. Methylene blue (MB) was used as a model drug to evaluate the potential application of the fibers for drug delivery. The release of MB was controlled in a nonbuffered medium by changing the pH of the solution. The sustained release of MB in a phosphate buffered saline (PBS) solution was achieved by constructing perfluorosilane networks on the fiber surfaces as capping layers. Temperature controlled release of MB was obtained by depositing temperature sensitive PAA/poly(N-isopropylacrylamide) (PNIPAAM) multilayers onto the fiber surfaces. The controlled release of drugs from electrospun fibers have potential applications as drug carriers in biomedical science.

  9. Charge regulation and local dielectric function in planar polyelectrolyte brushes.

    Science.gov (United States)

    Kumar, Rajeev; Sumpter, Bobby G; Kilbey, S Michael

    2012-06-21

    Understanding the effect of inhomogeneity on the charge regulation and dielectric properties, and how it depends on the conformational characteristics of the macromolecules is a long-standing problem. In order to address this problem, we have developed a field-theory to study charge regulation and local dielectric function in planar polyelectrolyte brushes. The theory is used to study a polyacid brush, which is comprised of chains end-grafted at the solid-fluid interface, in equilibrium with a bulk solution containing monovalent salt ions, solvent molecules, and pH controlling acid. In particular, we focus on the effects of the concentration of added salt and pH of the bulk in determining the local charge and dielectric function. Our theoretical investigations reveal that the dipole moment of the ion-pairs formed as a result of counterion adsorption on the chain backbones play a key role in affecting the local dielectric function. For polyelectrolytes made of monomers having dipole moments lower than the solvent molecules, dielectric decrement is predicted inside the brush region. However, the formation of ion-pairs (due to adsorption of counterions coming from the dissociation of added salt) more polar than the solvent molecules is shown to increase the magnitude of the dielectric function with respect to its bulk value. Furthermore, an increase in the bulk salt concentration is shown to increase the local charge inside the brush region.

  10. Formation of Soft Nanoparticles via Polyelectrolyte Complexation: A Viscometric Study

    Directory of Open Access Journals (Sweden)

    Rondon Céline

    2014-05-01

    Full Text Available This paper describes the formation of soft nanoparticles resulting from electrostatically driven complexation of oppositely charged polyelectrolytes. The system was composed of a strong polyanion (polystyrene sulfonate, PSS and a weak polycation (poly(allylamine hydrochloride, PAH in large excess. Soft nanoparticles were obtained by pouring a PSS solution into a PAH one under constant stirring. The polyelectrolyte complexes (PEC were characterized through a viscometric study complemented by Dynamic Light Scattering (DLS, electrophoretic mobility and suspension turbidity measurements. PEC suspensions were centrifuged and by measuring the viscosity of the supernatant, we were able to estimate the free polycation concentration and hence the percentage of complexed polycation. We also measured the relative viscosity of the suspensions; from the estimated contribution of the PEC particles and of the polycation in excess, the average particle volume fraction was estimated. From all viscometric data, we could derive the evolution of the binding stoichiometry in PEC and of the effective particle volume fraction as a function of the mixing ratio (ratio of the cationic to anionic groups and of the pH. Our results emphasize the importance of charge accessibility in controlling both the stoichiometry and packing density of the complexes.

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

    Directory of Open Access Journals (Sweden)

    Xiaozheng Duan

    2013-06-01

    Full Text Available 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.

  12. The solvation and ion condensation properties for sulfonated polyelectrolytes in different solvents—a computational study

    Science.gov (United States)

    Smiatek, J.; Wohlfarth, A.; Holm, C.

    2014-02-01

    In contrast to the broad knowledge about aqueous polyelectrolyte solutions, less is known about the properties in aprotic and apolar solvents. We therefore investigate the behavior of sulfonated polyelectrolytes in sodium form in the presence of different solvents via all-atom molecular dynamics simulations. The results clearly reveal strong variations in ion condensation constants and polyelectrolyte conformations for different solvents like water, dimethyl sulfoxide (DMSO) and chloroform. The binding free energies of the solvent contacts with the polyelectrolyte groups validate the influence of different solvent qualities. With regard to the ion condensation behavior, the numerical findings show that the explicit values for the condensation constants depend on the preferential binding coefficient as derived by the evaluation of Kirkwood-Buff integrals. Surprisingly, the smallest ion condensation constant is observed for DMSO compared to water, whereas in the presence of chloroform, virtually no free ions are present, which is in good agreement to the donor number concept. In contrast to the results for the low condensation constants, the sodium conductivity in DMSO is smaller compared to water. We are able to relate this result to the observed smaller diffusion coefficient for the sodium ions in DMSO.

  13. INTERACTIONS BETWEEN CATIONIC POLYELECTROLYTE AND PULP FINES

    Directory of Open Access Journals (Sweden)

    Elina Orblin

    2011-05-01

    Full Text Available Papermaking pulps are a mixture of fibres, fibre fragments, and small cells (parenchyma or ray cells, usually called pulp fines. The interactions between pulp fines and a cationic copolymer of acrylamide and acryloxyethyltrimethyl ammonium chloride were investigated based on solid-liquid isotherms prepared under different turbulence, and subsequent advanced surface characterization using X-ray photoelectron spectroscopy (XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS. The surface charge and surface area of pulp fine substrates were measured by methylene blue sorption-XPS analysis and nitrogen adsorption combined with mercury porosimetry, respectively. The driving force behind polyelectrolyte adsorption was the amount of the surface anionic charge, whereas surface area appeared to be of less importance. Based on a comparison of solid-liquid and XPS sorption isotherms, different polyelectrolyte conformations were suggested, depending on the types of fines: A flatter conformation and partial cell-wall penetration of polyelectrolytes on kraft fines from freshly prepared pulp, and a more free conformation with extended loops and tails on lignocellulosic fines from recycled pulp. Additionally, ToF-SIMS imaging proved that recycled pulp fines contained residual de-inking chemicals (primarily palmitic acid salts that possibly hinder the electrostatic interactions with polyelectrolytes.

  14. BlockSolve v1.1: Scalable library software for the parallel solution of sparse linear systems

    Energy Technology Data Exchange (ETDEWEB)

    Jones, M.T.; Plassmann, P.E.

    1993-03-01

    BlockSolve is a software library for solving large, sparse systems of linear equations on massively parallel computers. The matrices must be symmetric, but may have an arbitrary sparsity structure. BlockSolve is a portable package that is compatible with several different message-passing pardigms. This report gives detailed instructions on the use of BlockSolve in applications programs.

  15. BlockSolve v1. 1: Scalable library software for the parallel solution of sparse linear systems

    Energy Technology Data Exchange (ETDEWEB)

    Jones, M.T.; Plassmann, P.E.

    1993-03-01

    BlockSolve is a software library for solving large, sparse systems of linear equations on massively parallel computers. The matrices must be symmetric, but may have an arbitrary sparsity structure. BlockSolve is a portable package that is compatible with several different message-passing pardigms. This report gives detailed instructions on the use of BlockSolve in applications programs.

  16. Mediating gel formation from structurally controlled poly(electrolytes) through multiple "head-to-body" electrostatic interactions.

    Science.gov (United States)

    Srour, Hassan; Ratel, Olivier; Leocmach, Mathieu; Adams, Emma A; Denis-Quanquin, Sandrine; Appukuttan, Vinukrishnan; Taberlet, Nicolas; Manneville, Sébastien; Majesté, Jean-Charles; Carrot, Christian; Andraud, Chantal; Monnereau, Cyrille

    2015-01-01

    Tuning the chain-end functionality of a short-chain cationic homopolymer, owing to the nature of the initiator used in the atom transfer radical polymerization (ATRP) polymerization step, can be used to mediate the formation of a gel of this poly(electrolyte) in water. While a neutral end group gives a solution of low viscosity, a highly homogeneous gel is obtained with a phosphonate anionic moiety, as characterized by rheometry and diffusion nuclear magnetic resonance (NMR). This novel type of supramolecular control over poly(electrolytic) gel formation could find potential use in a variety of applications in the field of electro-active materials.

  17. Size, flexibility, and scattering functions of semiflexible polyelectrolytes with excluded volume effects: Monte Carlo simulations and neutron scattering experiments

    DEFF Research Database (Denmark)

    Cannavacciuolo, L.; Sommer, C.; Pedersen, J.S.;

    2000-01-01

    We present a systematic Monte Carlo study of the scattering function S(q) of semiflexible polyelectrolytes at infinite dilution, in solutions with different concentrations of added salt. In the spirit of a theoretical description of polyelectrolytes in terms of the equivalent parameters, namely...... outlined in the Odijk-Skolnick-Fixman theory, in which the behavior of charged polymers is described only in terms of increasing local rigidity and excluded volume effects. Moreover, the Monte Carlo data are found to be in very good agreement with experimental scattering measurements with equilibrium...

  18. Catalytic membranes prepared using layer-by-layer adsorption of polyelectrolyte/metal nanoparticle films in porous supports.

    Science.gov (United States)

    Dotzauer, David M; Dai, Jinhua; Sun, Lei; Bruening, Merlin L

    2006-10-01

    Layer-by-layer adsorption of polyelectrolytes and gold nanoparticles within porous supports provides a convenient method for forming catalytic membranes. The polyelectrolyte film effectively immobilizes the gold nanoparticles without inhibiting access to catalytic sites, as shown by the similar rate constants for nanoparticle-catalyzed 4-nitrophenol reduction in solution and in membranes. Modified alumina membranes reduce >99% of 0.4 mM 4-nitrophenol at linear flow rates of 0.98 cm/s, and the modification process is also applicable to track-etched polycarbonate supports.

  19. Huge Differences in the Kinetics of Swelling Enhancement and De-enhancement of Permanently Charged Polyelectrolyte Brushes.

    Science.gov (United States)

    Chu, Xiao; Yang, Jingfa; Zhao, Jiang

    2016-10-06

    As demonstrated previously (X. Chu et al., Soft Matter 2014, 10, 5568), permanently charged polyelectrolyte brushes can experience an enhancement of swelling by exposure to an external monovalent salt solution in moderate concentrations. Beyond the previous static measurements, the kinetics of the swelling enhancement and de-enhancement were investigated in the current study by using a quartz crystal microbalance with dissipation (QCM-D). By developing an effective approach to quantify the response in QCM-D, a vast difference in swelling enhancement and de-enhancement of a model permanently charged polyelectrolyte brush (sodium polystyrene sulfonate, NaPSS) was discovered. The results indicate new physics of the charged brushes: the difference in the attachment and detachment of counterions to the polyelectrolyte chains.

  20. Solubilization and separation of p-tert-butylphenol using polyelectrolyte/surfactant complexes in colloid-enhanced ultrafiltration

    Energy Technology Data Exchange (ETDEWEB)

    Uchiyama, Hirotaka; Christian, S.D.; Tucker, E.E.; Scamehorn, J.F. (Univ. of Oklahoma, Norman, OK (United States))

    1994-03-15

    Water-soluble polyelectrolyte/surfactant complexes, involving oppositely charged species, can form at quite low thermodynamic activities of the surfactant. This fact can be exploited in colloid-enhanced ultrafiltration separations, where both molecular organic pollutants and toxic ions are to be removed from contaminated aqueous streams. Investigations have been made of (a) the solubilization and ultrafiltration of solutions of organic solutes in polymer/surfactant solutions, for comparison with studies of micellar surfactant solutions in the absence of added polymers; (b) the penetration of surfactant through the membrane (leakage of monomer) in dialysis and ultrafiltration experiments; and (c) the utility of polyelectrolytes as scavengers'' for surfactant species that-enter the permeate or filtrate in colloid-enhanced ultrafiltration separations. The polyelectrolyte chosen for the studies is sodium poly(styrenesulfonate) and the surfactant is cetylpyridinium chloride (hexadecylpyridinium chloride). A detailed study has been made of the solubilization and separation of p-tert-butylphenol in aqueous mixtures of sodium poly(styrenesulfonate) and cetylpyridinium chloride, at polyelectrolyte to surfactant mole ratios of two to one and three to one.

  1. Water distributions in polystyrene-block-poly[styrene-g-poly(ethylene oxide)] block grafted copolymer system in aqueous solutions revealed by contrast variation small angle neutron scattering study

    Science.gov (United States)

    Li, Xin; Hong, Kunlun; Liu, Yun; Shew, Chwen-Yang; Liu, Emily; Herwig, Kenneth W.; Smith, Gregory S.; Zhao, Junpeng; Zhang, Guangzhao; Pispas, Stergios; Chen, Wei-Ren

    2010-10-01

    We develop an experimental approach to analyze the water distribution around a core-shell micelle formed by polystyrene-block-poly[styrene-g-poly(ethylene oxide (PEO)] block copolymers in aqueous media at a fixed polymeric concentration of 10 mg/ml through contrast variation small angle neutron scattering (SANS) study. Through varying the D2O/H2O ratio, the scattering contributions from the water molecules and the micellar constituent components can be determined. Based on the commonly used core-shell model, a theoretical coherent scattering cross section incorporating the effect of water penetration is developed and used to analyze the SANS I(Q ). We have successfully quantified the intramicellar water distribution and found that the overall micellar hydration level increases with the increase in the molecular weight of hydrophilic PEO side chains. Our work presents a practical experimental means for evaluating the intramacromolecular solvent distributions of general soft matter systems.

  2. Environmentally friendly cellulose-based polyelectrolytes in wastewater treatment.

    Science.gov (United States)

    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.

  3. Polyelectrolyte Complexation: A Field-Theoretic Description of Phase Behavior

    Science.gov (United States)

    Audus, Debra; Fredrickson, Glenn

    2010-03-01

    Our research focuses on a type of polyelectrolyte complexation called complex coacervation where two oppositely charged polymers in solution phase separate to form a dense polymer phase, known as the coacervate, and a supernatant, which typically has very low concentrations of polymer. To understand the effects of various parameters on coacervation, we previously developed a simple analytic theory for flexible polymers and small ions, which reproduces many general experimental trends. However, this theory is only valid for symmetric oppositely charged polymers, which limits its direct applicability to many experimental systems. Consequently, we have extended this theory to describe more complicated experimental systems where salt concentrations are high, pH equilibria shift with the complexation process, polymer concentrations are highly asymmetric, and counterion condensation may play an important role. To validate the modified theory, we compare our predictions with an exhaustive study of the phase behavior of polyacrylic acid and polyallylamine hydrochloride.

  4. New polyaniline(PAni)-polyelectrolyte (PDDMAC) composites: Synthesis and applications

    Energy Technology Data Exchange (ETDEWEB)

    Prakash, S.; Rao, Chepuri R.K.; Vijayan, M. [Functional Materials Division, Central Electrochemical Research Institute, Karaikudi-630 006 (India)

    2008-07-20

    Conducting and electroactive polymer blends of polyaniline (PAni) with polyelectrolyte, poly(diallydimethylammoniumchloride) (PDDMAC) have been synthesized by an in situ polymerization method and the resulting composites have been characterized by FT-IR, UV-Vis, XRD, AFM and electrochemical techniques. The blends are conducting and electroactive with even lower loadings of PAni and can be cast as films. The conductivity of the cast films containing 0.04-1.5 wt% PAni ranged from 4.5 x 10{sup -6} to 42 x 10{sup -6} S/cm. Some of the composites are tested for their corrosion inhibition property for pure iron in 1 M HCl solutions and were found to be active inhibitors. (author)

  5. Polystyrene-Poly(sodium methacrylate) Amphiphilic Block Copolymers by ATRP : Effect of Structure, pH, and Ionic Strength on Rheology of Aqueous Solutions

    NARCIS (Netherlands)

    Raffa, Patrizio; Brandenburg, Piter; Wever, Diego A. Z.; Broekhuis, Antonius A.; Picchioni, Francesco

    2013-01-01

    Three well-defined polystyrene-poly(sodium methacrylate) amphiphilic block copolymers characterized by different molecular architecture (diblock, triblock, and four-arm star) have been synthesized by ATRP. The rheology of their water solutions has been evaluated by measuring dynamic moduli and shear

  6. Polyelectrolyte Microcapsules: Ion Distributions from a Poisson-Boltzmann Model

    Science.gov (United States)

    Tang, Qiyun; Denton, Alan R.; Rozairo, Damith; Croll, Andrew B.

    2014-03-01

    Recent experiments have shown that polystyrene-polyacrylic-acid-polystyrene (PS-PAA-PS) triblock copolymers in a solvent mixture of water and toluene can self-assemble into spherical microcapsules. Suspended in water, the microcapsules have a toluene core surrounded by an elastomer triblock shell. The longer, hydrophilic PAA blocks remain near the outer surface of the shell, becoming charged through dissociation of OH functional groups in water, while the shorter, hydrophobic PS blocks form a networked (glass or gel) structure. Within a mean-field Poisson-Boltzmann theory, we model these polyelectrolyte microcapsules as spherical charged shells, assuming different dielectric constants inside and outside the capsule. By numerically solving the nonlinear Poisson-Boltzmann equation, we calculate the radial distribution of anions and cations and the osmotic pressure within the shell as a function of salt concentration. Our predictions, which can be tested by comparison with experiments, may guide the design of microcapsules for practical applications, such as drug delivery. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

  7. Mechanical Reinforcement of Wool Fiber through Polyelectrolyte Complexation with Chitosan and Gellan Gum

    Directory of Open Access Journals (Sweden)

    Khairul Anuar Mat Amin

    2013-10-01

    Full Text Available The formation of polyelectrolyte complex (PEC wool fibers formed by dipping chitosan or gellan gum-treated wool fibers into biopolymer solutions of opposite charge is reported. Treating wool fibers with chitosan (CH and gellan gum (GG solutions containing food dyes resulted in improved mechanical characteristics compared to wool fibers. In contrast, pH modification of the solutions resulted in the opposite effect. The mechanical characteristics of PEC-treated fibers were affected by the order of addition, i.e., dipping GG-treated fibers into chitosan resulted in mechanical reinforcement, whereas the reverse-order process did not.

  8. Rational synthesis of low-polydispersity block copolymer vesicles in concentrated solution via polymerization-induced self-assembly

    NARCIS (Netherlands)

    Gonzato, Carlo; Semsarilar, Mona; Jones, Elizabeth R.; Li, Feng; Krooshof, Gerard J P; Wyman, Paul; Mykhaylyk, Oleksandr O.; Tuinier, Remco; Armes, Steven P.

    2014-01-01

    Block copolymer self-assembly is normally conducted via post-polymerization processing at high dilution. In the case of block copolymer vesicles (or "polymersomes"), this approach normally leads to relatively broad size distributions, which is problematic for many potential applications. Herein we r

  9. CaSO4 and cationic polyelectrolyte as possible pectin precipitants in sugar beet juice clarification

    Directory of Open Access Journals (Sweden)

    Kuljanin Tatjana

    2015-01-01

    Full Text Available Three pectin preparations were isolated from fresh sugar beet pulp during the 150 minutes of extraction, at pH values of 1, 3.5 and 8.5. CaSO4 precipitant was added to 100 cm3 of 0.1% (wt solution of pectin. Studies were performed with 9 different concentrations of CaSO4 solution (50-450 mg dm-3 with the addition of a cationic polyelectrolyte (cationic PAM in concentrations of 3 and 5 mg dm-3. The efficiency of pectin precipitation was monitored by measuring the zeta potential of pectin preparations. Optimal amounts of precipitant CaSO4, without the use of a cationic polyelectrolyte, were as follows: 490-678 mg CaSO4/g pectin. After the use of a cationic polyelectrolyte, the optimal amounts of CaSO4 were smaller (353-512 mg/g pectin. These quantities are significantly lower than the average amount of CaO used in the conventional clarification process of sugar beet juice (about 9 g/g pectin of sugar beet juice. [Projekat Ministarstva nauke Republike Srbije, br. TR -31055

  10. Persistence length of a polyelectrolyte in salty water: Monte Carlo study.

    Science.gov (United States)

    Nguyen, T T; Shklovskii, B I

    2002-08-01

    We address the long standing problem of the dependence of the electrostatic persistence length l(e) of a flexible polyelectrolyte (PE) on the screening length r(s) of the solution within the linear Debye-Hückel theory. The standard Odijk, Skolnick, and Fixman (OSF) theory suggests l(e) proportional, variant r(2)s, while some variational theories and some computer simulations suggest l(e) proportional, variant r(s). In this paper, we use Monte Carlo simulations to study the conformation of a simple polyelectrolyte. Using four times longer PEs than in previous simulations and refined methods for the treatment of the simulation data, we show that the results are consistent with the OSF dependence l(e) proportional, variant r(2)s. The linear charge density of the PE, which enters in the coefficient of this dependence is properly renormalized to take into account local fluctuations.

  11. Lipophilic polyelectrolyte gels as super-absorbent polymers for nonpolar organic solvents.

    Science.gov (United States)

    Ono, Toshikazu; Sugimoto, Takahiro; Shinkai, Seiji; Sada, Kazuki

    2007-06-01

    Polyelectrolyte gels that are known as super-absorbent polymers swell and absorb water up to several hundred times their dried weights and have become ubiquitous and indispensable materials in many applications. Their superior swelling abilities originate from the electrostatic repulsion between the charges on the polymer chains and the osmotic imbalance between the interior and exterior of the gels. However, no super-absorbent polymers for volatile organic compounds (VOCs), and especially for nonpolar organic solvents (epsilonpolymer networks. This expands the potential of polyelectrolytes that have been used only in aqueous solutions or highly polar solvents, and provides soft materials that swell in a variety of media. These materials could find applications as protective barriers for VOCs spilled in the environment and as absorbents for waste oil.

  12. Local pH and effective pKA of weak polyelectrolytes - insights from computer simulations.

    Science.gov (United States)

    Nová, Lucie; Uhlík, Filip; Košovan, Peter

    2017-03-09

    In this work we study the titration behavior of weak polyelectrolytes by computer simulations. We analyze the local pH near the chains at various conditions and provide molecular-level insight which complements the recent experimental determination of this quantity. Next, we analyze the non-ideal titration behaviour of weak polyelectrolytes in solution, calculate the effective ionization constant and compare the simulation results with theoretical predictions. In contrast with the universal behaviour with respect to chain length, we find non-universality and deviations from theory with respect to polymer concentration and permittivity of the solvent. The latter we explain in terms of counterion condensation and ion correlation effects, which lead to reversal of the non-ideal titration behaviour at very low permittivities. We discuss the impact of these findings on the interpretation of experimental results.

  13. Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

    KAUST Repository

    Dorin, Rachel Mika

    2012-05-15

    Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

  14. Precipitate-Coacervate Transformation in Polyelectrolyte-Mixed Micelle Systems.

    Science.gov (United States)

    Comert, Fatih; Nguyen, Duy; Rushanan, Marguerite; Milas, Peker; Xu, Amy Y; Dubin, Paul L

    2017-05-04

    The polycation/anionic-nonionic mixed micelle, poly(diallyldimethylammonium chloride)-sodium dodecyl sulfate/Triton X-100 (PDADMAC-SDS/TX100), is a model polyelectrolyte-colloid system in that the micellar mole fraction of SDS (Y) controls the micelle surface charge density, thus modulating the polyelectrolyte-colloid interaction. The exquisite temperature dependence of this system provides an important additional variable, controlling both liquid-liquid (L-L) and liquid-solid (L-S) phase separation, both of which are driven by the entropy of small ion release. In order to elucidate these transitions, we applied high-precision turbidimetry (±0.1 %), isothermal titration calorimetry, and epifluorescence microscopy which demonstrates preservation of micelle structure under all conditions. The L-S region at large Y including precipitation displays a remarkable linear, inverse Y-dependence of the L-S transition temperature Ts. In sharp contrast, the critical temperature for L-L coacervation Tφ, shows nearly symmetrical effects of positive and negative deviations in Y from the point of soluble complex neutrality, which is controlled in solution by the micelle charge and the number of micelles bound per polymer chain n (Zcomplex = Zpolymer + nZmicelle). In solid-like states, n no longer signifies the number of micelles bound per polymer chain, since the proximity of micelles inverts the host-guest relationship with each micelle binding multiple PE chains. This intimate binding goes hand-in-hand with the entropy of release of micelle-localized charge-compensating ions whose concentration depends on Y. These ions need not be released in L-L coacervation, but during L-S transition their displacement by PE accounts for the inverse dependence of Ts on micelle charge, Y.

  15. Stabilization of protein-loaded starch microgel by polyelectrolytes

    NARCIS (Netherlands)

    Li, Y.; Norde, W.; Kleijn, J.M.

    2012-01-01

    The interaction of biocompatible polyelectrolytes (chargeable poly(amino acids)) with oxidized starch microgel particles has been studied. The aim was to form a polyelectrolyte complex layer around the outer shell of microgel particles filled with functional ingredients to slow down the release of

  16. Stabilization of Protein-Loaded Starch Microgel by Polyelectrolytes

    NARCIS (Netherlands)

    Li, Yuan; Norde, Willem; Kleijn, J. Mieke

    2012-01-01

    The interaction of biocompatible polyelectrolytes (chargeable poly(amino acids)) with oxidized starch microgel particles has been studied. The aim was to form a polyelectrolyte complex layer around the outer shell of microgel particles filled with functional ingredients to slow down the release of

  17. Weak polyelectrolyte multilayers as tunable membranes for solvent resistant nanofiltration

    NARCIS (Netherlands)

    Ilyas, Shazia; Joseph, Nithya; Szymczyk, Anthony; Volodin, Alexander; Nijmeijer, Kitty; Vos, de Wiebe M.; Vankelecom, Ivo F.J.

    2016-01-01

    This manuscript encompasses the investigation into the solvent resistant nanofiltration (SRNF) performance of multilayer membranes prepared from weak polyelectrolytes. These weak polyelectrolytes are unique in that the charge density is not fixed and depends on the coating pH, adding an extra variab

  18. Preparation of a disulfide-linked precipitative soluble support for solution-phase synthesis of trimeric oligodeoxyribonucleotide 3´-(2-chlorophenylphosphate building blocks

    Directory of Open Access Journals (Sweden)

    Amit M. Jabgunde

    2015-09-01

    Full Text Available The preparation of a disulfide-tethered precipitative soluble support and its use for solution-phase synthesis of trimeric oligodeoxyribonucleotide 3´-(2-chlorophenylphosphate building blocks is described. To obtain the building blocks, N-acyl protected 2´-deoxy-5´-O-(4,4´-dimethoxytritylribonucleosides were phosphorylated with bis(benzotriazol-1-yl 2-chlorophenyl phosphate. The “outdated” phosphotriester strategy, based on coupling of PV building blocks in conjunction with quantitative precipitation of the oligodeoxyribonucleotide with MeOH is applied. Subsequent release of the resulting phosphate and base-protected oligodeoxyribonucleotide trimer 3’-pTpdCBzpdGibu-5’ as its 3’-(2-chlorophenyl phosphate was achieved by reductive cleavage of the disulfide bond.

  19. Preparation of a disulfide-linked precipitative soluble support for solution-phase synthesis of trimeric oligodeoxyribonucleotide 3´-(2-chlorophenylphosphate) building blocks

    Science.gov (United States)

    Molina, Alejandro Gimenez; Virta, Pasi; Lönnberg, Harri

    2015-01-01

    Summary The preparation of a disulfide-tethered precipitative soluble support and its use for solution-phase synthesis of trimeric oligodeoxyribonucleotide 3´-(2-chlorophenylphosphate) building blocks is described. To obtain the building blocks, N-acyl protected 2´-deoxy-5´-O-(4,4´-dimethoxytrityl)ribonucleosides were phosphorylated with bis(benzotriazol-1-yl) 2-chlorophenyl phosphate. The “outdated” phosphotriester strategy, based on coupling of PV building blocks in conjunction with quantitative precipitation of the oligodeoxyribonucleotide with MeOH is applied. Subsequent release of the resulting phosphate and base-protected oligodeoxyribonucleotide trimer 3’-pTpdCBzpdGibu-5’ as its 3’-(2-chlorophenyl phosphate) was achieved by reductive cleavage of the disulfide bond. PMID:26664575

  20. Adsorption of polyelectrolyte on the surface of ZnO nanoparticles and the stability of colloidal dispersions

    Institute of Scientific and Technical Information of China (English)

    LIUFU Shengcong; XIAO Hanning; LI Yuping

    2005-01-01

    The present study focuses on the adsorption of a polyelectrolyte, the component of which is a polymer of maleic anhydride sodium salt, on the surface of nanometric zinc oxide particles and the colloidal stability of aqueous dispersions. FTIR spectroscopic data provided evidence in support of hydrogen bonding and chemical interaction in the case of the polyelectrolyte-ZnO system. The adsorption isotherms showed the influences of polyelectrolyte concentration, pH and ionic strength on the adsorption. With the increase of pH the saturated adsorbed amount decreased, while the thickness of adsorption layer increased. The saturated adsorbed amount increased with increasing salt concentration, and decreased with further increasing salt concentration. It should be noted that in the presence of a CaCl2 solution the adsorbed amount and the adsorption layer thickness were greater than those in the NaCl solution of the same concentration. The change of the absorbance of zinc oxide dispersions showed that the absorbance decreased slowly at high pH. There was a maximum point for the absorbance of the zinc oxide dispersions in the presence of various polyelectrolyte concentrations. The change of dispersion stability resulted from the change of macromolecular chains conformation at the interface.

  1. Influence of the Hydrophobicity of Polyelectrolytes on Polyelectrolyte Complex Formation and Complex Particle Structure and Shape

    Directory of Open Access Journals (Sweden)

    Gudrun Petzold

    2011-08-01

    Full Text Available Polyelectrolyte complexes (PECs were prepared by structural uniform and strongly charged cationic and anionic modified alternating maleic anhydride copolymers. The hydrophobicity of the polyelectrolytes was changed by the comonomers (ethylene, isobutylene and styrene. Additionally, the n−/n+ ratio of the molar charges of the polyelectrolytes and the procedure of formation were varied. The colloidal stability of the systems and the size, shape, and structure of the PEC particles were investigated by turbidimetry, dynamic light scattering (DLS and atomic force microscopy (AFM. Dynamic light scattering indicates that beside large PEC particle aggregates distinct smaller particles were formed by the copolymers which have the highest hydrophobicity (styrene. These findings could be proved by AFM. Fractal dimension (D, root mean square (RMS roughness and the surface profiles of the PEC particles adsorbed on mica allow the following conclusions: the higher the hydrophobicity of the polyelectrolytes, the broader is the particle size distribution and the minor is the swelling of the PEC particles. Hence, the most compact particles are formed with the very hydrophobic copolymer.

  2. New polyelectrolyte complex particles as colloidal dispersions based on weak synthetic and/or natural polyelectrolytes

    Directory of Open Access Journals (Sweden)

    2011-06-01

    Full Text Available This study aims to evidence the formation of stable polyelectrolyte complex particles as colloidal dispersions using some weak polyelectrolytes: chitosan and poly(allylamine hydrochloride as polycations and poly(acrylic acid (PAA and poly(2-acrylamido-2-methylpropanesulfonic acid – co – acrylic acid (PAMPSAA as polyanions. Polyelectrolyte complex particles as colloidal dispersion were prepared by controlled mixing of the oppositely charged polymers, with a constant addition rate. The influences of the polyelectrolytes structure and the molar ratio between ionic charges on the morphology, size, and colloidal stability of the complex particles have been deeply investigated by turbidimetry, dynamic light scattering and atomic force microscopy. A strong influence of polyanion structure on the values of molar ratio n–/n+ when neutral complex particles were obtained has been noticed, which shifts from the theoretical value of 1.0, observed when PAA was used, to 0.7 for PAMPSAA based complexes. The polyions chain characteristics influenced the size and shape of the complexes, larger particles being obtained when chitosan was used, for the same polyanion, and when PAMPSAA was used, for the same polycation.

  3. Rheological Behavior of the Guanidio Polyelectrolytes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yu-mei; JIANG Jian-ming; CHEN Yan-mo

    2002-01-01

    The rheological behavior of polyhexamethylene guanidine hydrochloride (PHGC) and polyethylene guanidine stearate (PHGS) has been investigated using the capillary rheometer. It is shown that the polyelectrolyte melts are non-Newtonian of shear. thinning fluid. The melt viscosity, the flow activation energy and the flow temperature are high even if the molecular weight is not high. The melting viscosity of PHGC is higher than that of PHGS at the same experimental conditions. By comparison with the case of PHGS the non-Newtonian index of PHGC is smaller, the flow activation energy and the flow temperature of PHGC are higher, which was caused by the difference in their molecular structure.

  4. Theory of polyelectrolyte complexation—Complex coacervates are self-coacervates

    Science.gov (United States)

    Delaney, Kris T.; Fredrickson, Glenn H.

    2017-06-01

    The complexation of mixtures of cationic and anionic polymers to produce complex-coacervate phases is a subject of fundamental importance to colloid and polymer science as well as to applications including drug delivery, sensing technologies, and bio-inspired adhesives. Unfortunately the theoretical underpinnings of complex coacervation are widely misunderstood and conceptual mistakes have propagated in the literature. Here, a simple symmetric polyelectrolyte mixture model in the absence of salt is used to discuss the salient features of the phase diagram, including the location of the critical point, binodals, and spinodals. It is argued that charge compensation by dimerization in the dilute region renders the phase diagram of an oppositely charged polyelectrolyte mixture qualitatively and quantitatively similar to that of a single-component symmetric diblock polyampholyte solution, a system capable of "self-coacervation." The theoretical predictions are verified using fully fluctuating field-theoretic simulations for corresponding polyelectrolyte and diblock polyampholyte models. These represent the first comprehensive, approximation-free phase diagrams for coacervate and self-coacervate systems to appear in the literature.

  5. BlockSolve95 users manual: Scalable library software for the parallel solution of sparse linear systems

    Energy Technology Data Exchange (ETDEWEB)

    Jones, M.T.; Plassmann, P.E.

    1995-12-01

    BlockSolve95 is a software library for solving large, sparse systems of linear equations on massively parallel computers or networks of workstations. The matrices must be symmetric in structure; however, the matrix nonzero values may be either symmetric or nonsymmetric. The nonzeros must be real valued. BlockSolve95 uses a message-passing paradigm and achieves portability through the use of the MPI message-passing standard. Emphasis has been placed on achieving both good professor performance through the use of higher-level BLAS and scalability through the use of advanced algorithms. This report gives detailed instructions on the use of BlockSolve95 and descriptions of a number of program examples that can be used as templates for application programs.

  6. Triclosan loaded electrospun nanofibers based on a cyclodextrin polymer and chitosan polyelectrolyte complex.

    Science.gov (United States)

    Ouerghemmi, Safa; Degoutin, Stéphanie; Tabary, Nicolas; Cazaux, Frédéric; Maton, Mickaël; Gaucher, Valérie; Janus, Ludovic; Neut, Christel; Chai, Feng; Blanchemain, Nicolas; Martel, Bernard

    2016-11-20

    This work focuses on the relevance of antibacterial nanofibers based on a polyelectrolyte complex formed between positively charged chitosan (CHT) and an anionic hydroxypropyl betacyclodextrin (CD)-citric acid polymer (PCD) complexing triclosan (TCL). The study of PCD/TCL inclusion complex and its release in dynamic conditions, a cytocompatibility study, and finally the antibacterial activity assessment were studied. The fibers were obtained by electrospinning a solution containing chitosan mixed with PCD/TCL inclusion complex. CHT/TCL and CHT-CD/TCL were also prepared as control samples. The TCL loaded nanofibers were analyzed by Scanning Electron Microscopy (SEM), Fourier Transformed Infrared spectroscopy (FTIR) and X-Ray Diffraction (XRD). Nanofibers stability and swelling behavior in aqueous medium were pH and CHT:PCD weight ratio dependent. Such results confirmed that CHT and PCD interacted through ionic interactions, forming a polyelectrolyte complex. A high PCD content in addition to a thermal post treatment at 90°C were necessary to reach a nanofibers stability during 15days in soft acidic conditions, at pH=5.5. In dynamic conditions (USP IV system), a prolonged release of TCL with a reduced burst effect was observed on CHT-PCD polyelectrolyte complex based fibers compared to CHT-CD nanofibers. These results were confirmed by a microbiology study showing prolonged antibacterial activity of the nanofibers against Escherichia coli and Staphylococcus aureus. Such results could be explained by the fact that the stability of the polyelectrolyte CHT-PCD complex in the nanofibers matrix prevented the diffusion of the PCD/triclosan inclusion complex in the supernatant, on the contrary of the similar system including cyclodextrin in its monomeric form.

  7. Fundamentals of tri-block copolymer self-assembly in solutions, and its relation to nano-templating

    NARCIS (Netherlands)

    Denkova, A.G.

    2009-01-01

    The purpose of this thesis is to obtain a better understanding of the formation mechanism of mesoporous silica materials, such as SBA-15 that use block copolymers as templating agents. Despite the fact that these materials are now extensively synthesized, the fundamental role of the different synthe

  8. Development of Highly-Conductive Polyelectrolytes for Lithium Batteries

    Science.gov (United States)

    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

  9. Modeling competitive substitution in a polyelectrolyte complex

    Energy Technology Data Exchange (ETDEWEB)

    Peng, B.; Muthukumar, M., E-mail: muthu@polysci.umass.edu [Department of Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, Massachusetts 01003 (United States)

    2015-12-28

    We have simulated the invasion of a polyelectrolyte complex made of a polycation chain and a polyanion chain, by another longer polyanion chain, using the coarse-grained united atom model for the chains and the Langevin dynamics methodology. Our simulations reveal many intricate details of the substitution reaction in terms of conformational changes of the chains and competition between the invading chain and the chain being displaced for the common complementary chain. We show that the invading chain is required to be sufficiently longer than the chain being displaced for effecting the substitution. Yet, having the invading chain to be longer than a certain threshold value does not reduce the substitution time much further. While most of the simulations were carried out in salt-free conditions, we show that presence of salt facilitates the substitution reaction and reduces the substitution time. Analysis of our data shows that the dominant driving force for the substitution process involving polyelectrolytes lies in the release of counterions during the substitution.

  10. Fluorescent Polystyrene Sulfonate for Polyelectrolyte Studies

    Science.gov (United States)

    Huberty, Wayne; Tong, Xiaowei; Balamurugan, Sreelatha; Zhang, Donghui; Russo, Paul

    2012-02-01

    The slow-mode decay found by dynamic light scattering for polyelectrolytes in low-salt conditions has perplexed investigators since its first observation. Many characterization methods have suggested temporary or transient aggregation, although there is still no consensus on the cause. Many different polyelectrolytes demonstrate the slow-mode decay, but the sodium salt of polystyrene sulfonate (NaPSS) is the most popular choice for study. Commercially available NaPSS may have hydrophobic patches due to incomplete sulfonation leading to associations apart from any putative ionic mechanisms. Therefore, essentially full sulfonation, or ``patchless'', NaPSS should be synthesized. To facilitate fluorescence measurements, which can provide new insights to the slow-mode phenomenon, the material must be rendered fluorescent (F-NaPSS). Several approaches to F-NaPSS have appeared; some labeled a previously synthesized NaPSS without concern for its hydrophobic patches. Other strategies include a free radical copolymerization of styrene sulfonate and a vinyl amine to provide side chains viable for labeling. This method is successful, but yields only small amounts of nearly monodisperse polymer after fractionation. In this presentation, a high-yield synthesis of fully sulfonated, low-polydispersity, fluorescently tagged polymer will be discussed.

  11. Characterization of Responsive Hydrogel Nanoparticles upon Polyelectrolyte Complexation

    Directory of Open Access Journals (Sweden)

    Su-Kyoung Lee

    2017-02-01

    Full Text Available Characterization of responsive hydrogels and their interaction with other molecules have significantly expanded our understanding of the functional materials. We here report on the response of poly(N-isopropylacrylamide-co-acrylic acid (pNIPAm-co-AAc nanogels to the addition of the poly(allylamine hydrochloride (PAH in aqueous dispersions. We find that the hydrodynamic radius and stability of nanogels are dependent on the PAH/nanogel stoichiometry. If the nanogel solution is titrated with very small aliquots of PAH, the nanogels decrease in radius until the equivalence point, followed by aggregation at suprastoichiometric PAH additions. Conversely, when titrated with large aliquots, the nanogel charge switches rapidly from anionic to cationic, and no aggregation is observed. This behavior correlates well with electrophoretic mobility measurements, which shows the nanogel charge transitioning from negative to positive upon PAH addition. The volume phase transition temperature (VPTT of the nanogels is also measured to discover the effect of polyelectrolyte complexation on the deswelling thermodynamics. These data show that charge neutralization upon PAH addition decreases the VPTT of the nanogel at pH 6.5. However, if an excess amount of PAH is added to the nanogel solution, the VPTT shifts back to higher temperatures due to the formation of a net positive charge in the nanogel network.

  12. Nanoparticle gel electrophoresis: bare charged spheres in polyelectrolyte hydrogels.

    Science.gov (United States)

    Li, Fei; Hill, Reghan J

    2013-03-15

    Nanoparticle gel electrophoresis has recently emerged as an attractive means of separating and characterizing nanoparticles. Consequently, a theory that accounts for electroosmotic flow in the gel, and coupling of the nanoparticle and hydrogel electrostatics and hydrodynamics, is required, particularly for gels in which the mesh size is comparable to or smaller than the particle radii. Here, we present an electrokinetic model for charged, spherical colloidal particles undergoing electrophoresis in charged (polyelectrolyte) hydrogels: the gel-electrophoresis analogue of Henry's theory for electrophoresis in Newtonian electrolytes. We compare numerically exact solutions of the model with several independent asymptotic approximations, identifying regions in the parameter space where these approximations are accurate or break down. As previously assumed in the literature, Henry's formula, modified by the addition of a constant electroosmotic flow mobility, is accurate only for nanoparticles that are small compared to the hydrogel mesh size. We derived an exact analytical solution of the full model by judiciously modifying the theory of Allison et al. for uncharged gels, drawing on the superposition methodology of Doane et al. to account for hydrogel charge. This furnishes accurate and economical mobility predictions for the entire parameter space. The present model suggests that nanoparticle size separations (with diameters ≲40 nm) are optimal at low ionic strength, with a gel mesh size that is selected according to the particle charging mechanism. For weakly charged particles, optimal size separation is achieved when the Brinkman screening length is matched to the mean particle size. Copyright © 2012 Elsevier Inc. All rights reserved.

  13. Functional polyelectrolyte multilayer membranes for water purification applications

    Energy Technology Data Exchange (ETDEWEB)

    Tripathi, Bijay P., E-mail: bijayptripathi@yahoo.com [Department of Nanostructured Materials, Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden (Germany); Dubey, Nidhi C. [Department of Nanostructured Materials, Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden (Germany); Technische Universität Dresden, Department of Chemistry, 01069 Dresden (Germany); Stamm, M., E-mail: stamm@ipfdd.de [Department of Nanostructured Materials, Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden (Germany); Technische Universität Dresden, Department of Chemistry, 01069 Dresden (Germany)

    2013-05-15

    Highlights: ► LBL film on the surface and in to the pores was prepared via flow through method. ► The membranes showed high rejection of Congo Red with sufficiently high flux. ► High antifouling ability in terms of both organic and bio fouling was observed. -- Abstract: A diverse set of supported multilayer assemblies with controllable surface charge, hydrophilicity, and permeability to water and solute was fabricated by pressure driven permeation of poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDDA) solution through poly(ethylene terephthalate) (PET) track-etched membranes. The polyelectrolyte multilayer fabrication was confirmed by means of FTIR, SEM, AFM, ellipsometry, zetapotential, and contact angle characterization. The prepared membranes were characterized in terms of their pure water permeability, flux recovery, and resistance to organic and biofouling properties. The antifouling behavior of the membranes was assessed in terms of protein adsorption and antibacterial behavior. Finally, the membranes were tested for rejection of selected water soluble dyes to establish their usefulness for organic contaminant removal from water. The membranes were highly selective and capable of nearly complete rejection of congo red with sufficiently high fluxes. The feasibility of regenerating the prepared membranes fouled by protein was also demonstrated and good flux recovery was obtained. In summary, the multilayer approach to surface and pore modification was shown to enable the design of membranes with the unique combination of desirable separation characteristics, regenerability of the separation layer, and antifouling behavior.

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

    Science.gov (United States)

    Sanyal, Oishi

    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.

  15. Dynamics of polyelectrolyte adsorption on surfaces: Applications in the detection of iron in water

    Science.gov (United States)

    Gammana, Madhira N.

    Layer by layer (LbL) self assembly is a simple multilayer thin (nanometer scale) film fabricating technique. The mechanism of film growth remains a topic of much controversy. For example, several models have been proposed to explain the origin of linear and exponential film growth that are attributed to differences in the dynamic processes that occur at the molecular level during film formation. The problem is that there are no methods that directly measure the dynamics of polymer formation during LbL film formation. In this thesis, I describe the essential elements of an ATR-IR spectroscopic method that was developed to enable measurement of the dynamics of the mass adsorbed and polyelectrolyte conformation during the formation of PEM's. In particular, I followed the sequential adsorption of Sodium polyacrylate (NaPA) and Poly (diallyldimethylammonium) chloride (PDADMAC) from deionized (DI) water and as a function of ionic strength to show that polymer diffusion occurs between layers when adsorbed from DI water. In contrast, a denser layer occurs with no polymer interdiffusion for deposition from 0.02M ionic strength solutions of NaPA and PDADMAC. While the mass deposited increased with ionic strength, linear multilayer growth in films were observed in all cases. This finding disputes a common viewpoint that interdiffusion of polymer layers is a key feature of exponential film growth. The theme of polymer layer adsorption was used in the detection of Fe 3+ in seawater. A new approach, developed previously in Tripp's group, utilized "vertical amplification" in which a block copolymer assembled on membranes provided multiple anchoring points extending from the surface for attaching a siderophore, desferrioxamine B (DFB). The Fe3+ chelates with the siderophore producing a red color that can be quantified by visible spectroscopy. However, the rate of Fe3+ uptake was found to be dependent on flow rate. The origin of this flow rate dependence was identified by the work

  16. Self-Assembly of Double Hydrophilic Poly(2-ethyl-2-oxazoline-b-poly(N-vinylpyrrolidone Block Copolymers in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Jochen Willersinn

    2017-07-01

    Full Text Available The self-assembly of a novel combination of hydrophilic blocks in water is presented, namely poly(2-ethyl-2-oxazoline-b-poly(N-vinylpyrrolidone (PEtOx-b-PVP. The completely water-soluble double hydrophilic block copolymer (DHBC is formed via copper-catalyzed polymer conjugation, whereas the molecular weight of the PVP is varied in order to study the effect of block ratio on the self-assembly process. Studies via dynamic light scattering, static light scattering as well as microscopy techniques, e.g., cryo scanning electron microscopy or laser scanning confocal microscopy, show the formation of spherical particles in an aqueous solution with sizes between 300 and 400 nm. Particles of the DHBCs are formed without the influence of external stimuli. Moreover, the efficiency of self-assembly formation relies significantly on the molar ratio of the utilized blocks. The nature of the formed structures relies further on the concentration, and indications of particular and vesicular structures are found.

  17. Electrokinetics of pH-regulated zwitterionic polyelectrolyte nanoparticles

    Science.gov (United States)

    Yeh, Li-Hsien; Tai, Yi-Hsuan; Wang, Nan; Hsu, Jyh-Ping; Qian, Shizhi

    2012-11-01

    The electrokinetic behavior of pH-regulated, zwitterionic polyelectrolyte (PE) nanoparticles (NPs) in a general electrolyte solution containing multiple ionic species is investigated for the first time. The NPs considered are capable of simulating entities such as proteins, biomolecules, and synthetic polymers. The applicability of the model proposed is verified by the experimental data of succinoglycan nanoparticles available in the literature. We show that, in addition to their effective charge density, counterion condensation, double-layer polarization, and electro-osmotic flow of unbalanced counterions inside the double layer all significantly affect the electrophoretic behaviors of NPs. Our model successfully predicts many interesting electrophoretic behaviors, which qualitatively agree with experimental observations available in the literature. In contrast, because the effects of double-layer polarization and charge regulation are neglected, the existing theoretical models fail to explain the experimental results. The results gathered provide necessary information for the interpretation of relevant electrophoresis data in practice, and for nanofluidic applications such as biomimetic ion channels and nanopore-based sensing of single biomolecules.The electrokinetic behavior of pH-regulated, zwitterionic polyelectrolyte (PE) nanoparticles (NPs) in a general electrolyte solution containing multiple ionic species is investigated for the first time. The NPs considered are capable of simulating entities such as proteins, biomolecules, and synthetic polymers. The applicability of the model proposed is verified by the experimental data of succinoglycan nanoparticles available in the literature. We show that, in addition to their effective charge density, counterion condensation, double-layer polarization, and electro-osmotic flow of unbalanced counterions inside the double layer all significantly affect the electrophoretic behaviors of NPs. Our model successfully

  18. Polymer Physics Prize Lecture: Polyelectrolyte complexes: New routes to useful soft materials

    Science.gov (United States)

    Tirrell, Matthew

    2012-02-01

    Mixtures of oppositely charged polyelectrolytes may form precipitates (phase-separated solids) or coacervates (phase-separated fluids). Coacervates have been known for a long time to have interesting properties such as very low interfacial tension with water and a resultant ability to coat surfaces, engulf particles and invade porous media. Most prior work on coacervate complexes has been done with structurally complex (e.g., gum Arabic), biologically derived macromolecules (e.g., gelation). Our work is focusing on phase behavior and self-assembly in classes of structurally simpler polymers. Polypeptides are one such class, where we can produce anionic, cationic and neutral, water-soluble polymers all with the some backbone and varying in small side-group structures. We are able to demonstrate very general patterns in phase behavior over different members of this class of polymers. Coacervate formation is the rule rather than the exception in these materials, with such formation quite strongly peaked at balanced stoichiometry of the polyelectrolyte components. One molar salt is usually sufficient to dissolve the coacervate phases that form. Block copolymer mixtures containing oppositely charged blocks can form self-assembled structures: micelles with diblocks and hydrogels with triblocks. The structure and properties of these assemblies can be tuned based on knowledge of the bulk phase behavior response to molecular weight, stoichiometry and salt concentration. Examples of phase behavior and structure-property relationship will be discussed.

  19. IONIC SELF-ASSEMBLY AND HUMIDITY SENSITIVITY OF POLYELECTROLYTE MULTILAYERS

    Institute of Scientific and Technical Information of China (English)

    Hai-hu Yu; De-sheng Jiang

    2002-01-01

    Multilayer thin films of alternately adsorbed layers of polyelectrolytes PDDA and PS-119 were formed on both planar silica substrates and optical fibers through the ionic self-assembly technique. Intrinsic Fabry-Perot cavities were fabricated by stepwise assembling the polyelectrolytes onto the ends of optical fibers for the purposes of fiber optical device and sensor development. Ionically assembled polyelectrolyte multilayer thin films, in whichthere are hydrophilic side groups with strong affinity towards water molecules, are a category of humidity-sensitive functional materials. The polyelectrolyte multilayer thin film Fabry-Perot cavity-type fiber optical humidity sensor can work over a wide range from about 0% RH to about 100% RH with a response time less than 1 s.

  20. Effect of Supporting Polyelectrolyte Multilayers and Deposition Conditions on the Formation of 1-Palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine/1-Palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine Lipid Bilayers.

    Science.gov (United States)

    Wlodek, Magdalena; Szuwarzynski, Michal; Kolasinska-Sojka, Marta

    2015-09-29

    The formation of complete supported lipid bilayers by vesicle adsorption and rupture was studied in relation to deposition conditions of vesicles and underlying cushion formed from various polyelectrolytes. 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 of various pH with or without NaCl addition. Polyelectrolyte multilayer films (PEM) were constructed by sequential adsorption of alternately charged polyelectrolytes from their solutions-layer-by-layer deposition (LBL). The mechanism of the formation of supported lipid bilayer on polyelectrolyte films was studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). QCM-D allowed following the adsorption kinetics while AFM measurements verified the morphology of lipid vesicles and isolated bilayer patches on the PEM cushions providing local topological images in terms of lateral organization. Additionally, polyelectrolyte cushions were characterized with ellipsometry to find thickness and swelling properties, and their roughness was determined using AFM. It has been demonstrated that the pH value and an addition of NaCl in the buffer solution as well as the type of the polyelectrolyte cushion influence the kinetics of bilayer formation and the quality of formed bilayer patches.

  1. Block copolymer-mediated synthesis of gold nanoparticles in aqueous solutions: Segment effect on gold ion reduction, stabilization, and particle morphology

    OpenAIRE

    Sakai, Toshio; Horiuchi, Yuya; Alexandridis, Paschalis; Okada, Tomohiko; Mishima, Shozi

    2013-01-01

    We report here on the segment effects of poly(ethylene oxide)-containing block copolymers (PEO-BCP) on the reduction activity for tetrachloride gold(III) ([AuCl4](-)), interfacial activity for gold surface, colloidal stability, and morphology of gold nanoparticles formed in aqueous solutions. In particular, the effects of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), polyethylene (PE) segments and amino group (NH2) on the rate of [AuCl4](-) reduction, adsorption of PEO-BCP onto gol...

  2. Block copolymer-mediated synthesis of gold nanoparticles in aqueous solutions: Segment effect on gold ion reduction, stabilization, and particle morphology

    OpenAIRE

    Sakai, Toshio; Horiuchi, Yuya; Alexandridis, Paschalis; Okada, Tomohiko; Mishima, Shozi

    2013-01-01

    We report here on the segment effects of poly(ethylene oxide)-containing block copolymers (PEO-BCP) on the reduction activity for tetrachloride gold(III) ([AuCl4](-)), interfacial activity for gold surface, colloidal stability, and morphology of gold nanoparticles formed in aqueous solutions. In particular, the effects of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), polyethylene (PE) segments and amino group (NH2) on the rate of [AuCl4](-) reduction, adsorption of PEO-BCP onto gol...

  3. Effect of buprenorphine as an adjunct with plain local anesthetic solution in supraclavicular brachial plexus block on quality and duration of postoperative analgesia

    Directory of Open Access Journals (Sweden)

    Surekha Patil

    2015-01-01

    Full Text Available Background and Aims: Supraclavicular brachial plexus block is ideal for upper limb surgical procedures. Buprenorphine, an agonist antagonist opioid has been used as an adjunct to prolong analgesia. We aimed to evaluate the quality and duration of postoperative analgesia by addition of buprenorphine to local anesthetic solution. Material and Methods: A prospective, randomized, double-blind control study was conducted on 50 healthy patients of ASA Grade I/II of age group 20-70 years scheduled for orthopedic and reconstructive surgery of upper limb under supraclavicular brachial plexus block. Patients were allocated into two groups, 25 in each group viz.: Group B (buprenorphine group received 20 ml 0.5% bupivacaine + 15 ml 2% lignocaine with adrenaline (1:200,000 + 4 ml normal saline + 1500 units hyaluronidase + 3 μg/kg buprenorphine diluted to 1 ml normal saline. Group C (control group received 20 ml 0.5% bupivacaine + 15 ml 2% lignocaine with adrenaline (1:200,000 + 4 ml normal saline + 1500 units hyaluronidase + 1 ml normal saline. The parameters observed were onset and duration of sensory and motor block, quality and duration of analgesia and side-effects. Results: The mean duration of postoperative analgesia was significantly longer in Group B (16.04 ± 3.19 h than in Group C (6.20 ± 0.74 h. There was no difference between two groups on mean onset of sensory block. The mean duration motor block was significantly longer in Group B (4.93 ± 0.94 h than in Group C (2.25 ± 0.62 h [P < 0.05]. The mean duration of sensory block was also significantly longer in Group B (5.71 ± 0.94 h than in Group C (4.94 ± 0.70 h with P < 0.05. Conclusion: Addition of 3 μg/kg buprenorphine to 0.5% bupivacaine for supraclavicular brachial plexus block prolonged duration of postoperative analgesia and sensory blockade without an increase in side effects.

  4. Obtaining and characterization of thin films polyelectrolyte with gold nanoparticles; Obtencao e caracterizacao de filmes finos de polieletrolitos com nanoparticulas de ouro

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2011-07-01

    Thin films of polyelectrolytes are manufactured via sequential adsorption of weak polyelectrolytes from aqueous solutions based on electrostatic interaction of oppositely charged polymers. Metal containing polymeric compounds are of particular interest to the production of materials with electrical interface and optical properties. In this sense, the objective of this study was to obtain thin films of weak polyelectrolytes and analyze the distribution of gold nanoparticles stabilized by sodium citrate and by poly (vinylpyrrolidone). The characterization was performed using UV-visible, X-ray diffraction and atomic force microscopy. The techniques of UV-visible and X-ray diffraction was confirmed the presence of gold in the films, the atomic force microscopy images were used to analyze the morphology of the films and check the behavior of the diffusion of gold nanoparticles. (author)

  5. Deposition of polyelectrolyte multilayer films made from chitosan and xanthan on biodegradable substrate: Effect of pH and ionic strength

    Science.gov (United States)

    Viraneva, A.; Marudova, M.; Sotirov, S.; Bodurov, I.; Pilicheva, B.; Uzunova, Y.; Exner, G.; Grancharova, Ts.; Vlaeva, I.; Yovcheva, T.

    2016-03-01

    The aim of the present work is to investigate the effect of pH and ionic strength on the deposition of chitosan/xanthan multilayers on preliminary corona charged substrates from polylactic acid. The multilayer films were formed by alternative dipping the substrate into chitosan and xanthan polyelectrolyte solutions. For this purpose 0.1% chitosan solution and 0.05% xanthan solution in acetate buffers with pH 4; 4.5 and 5 and ionic strengths 0; 0.01; 0.1 and 1 mol/l were used. The film properties were investigated by FTIR, laser refractometry, XPS and AFM methods. It was found that the binding of the polyelectrolytes to the substrate was irreversible over the time of deposition. The investigated parameters were found to depend on both pH and ionic strength of the polyelectrolyte solutions. This behaviour was attributed to the changes in charge density of the polyelectrolytes and screening effect of the counterions.

  6. Polyelectrolyte Multilayers: Towards Single Cell Studies

    Directory of Open Access Journals (Sweden)

    Dmitry Volodkin

    2014-05-01

    Full Text Available Single cell analysis (SCA is nowadays recognized as one of the key tools for diagnostics and fundamental cell biology studies. The Layer-by-layer (LbL polyelectrolyte assembly is a rather new but powerful technique to produce multilayers. It allows to model the extracellular matrix in terms of its chemical and physical properties. Utilization of the multilayers for SCA may open new avenues in SCA because of the triple role of the multilayer film: (i high capacity for various biomolecules; (ii natural mimics of signal molecule diffusion to a cell and (iii cell patterning opportunities. Besides, light-triggered release from multilayer films offers a way to deliver biomolecules with high spatio-temporal resolution. Here we review recent works showing strong potential to use multilayers for SCA and address accordingly the following issues: biomolecule loading, cell patterning, and light-triggered release.

  7. Stereoregularity Drives Precipitation in Polyelectrolyte Complex Formation

    Science.gov (United States)

    Tirrell, Matthew; Perry, Sarah; Leon, Lorraine; Kade, Matthew; Priftis, Dimitris; Black, Katie; Hoffman, Kyle; Whitmer, Jonathan; Qin, Jian; de Pablo, Juan

    2014-03-01

    This study investigates the effect of stereoregularity on the formation of polypeptide-based complex formation and assembly into micelles, hydrogels and ordered phases. We demonstrate that fluid complex coacervate formation (rather than solid complex precipitation) between oppositely charged polypeptides requires at least one racemic partner in order to disrupt backbone hydrogen bonding networks and prevent the hydrophobic collapse of the polymers into compact, fibrillar secondary structures. Computer simulations bear this out and enable visualization of the molecular structure of the complexes. The ability to choose between conditions of fluid phase formation and solid phase formation is a useful tool in developing new self-assembled materials based on polyelectrolyte complex formation. Support from the Argonne National Laboratory Laboratory Research and Development Program (2011-217) is gratefully acknowledged.

  8. Novel cationic polyelectrolyte coatings for capillary electrophoresis.

    Science.gov (United States)

    Duša, Filip; Witos, Joanna; Karjalainen, Erno; Viitala, Tapani; Tenhu, Heikki; Wiedmer, Susanne K

    2016-01-01

    The use of bare fused silica capillary in CE can sometimes be inconvenient due to undesirable effects including adsorption of sample or instability of the EOF. This can often be avoided by coating the inner surface of the capillary. In this work, we present and characterize two novel polyelectrolyte coatings (PECs) poly(2-(methacryloyloxy)ethyl trimethylammonium iodide) (PMOTAI) and poly(3-methyl-1-(4-vinylbenzyl)-imidazolium chloride) (PIL-1) for CE. The coated capillaries were studied using a series of aqueous buffers of varying pH, ionic strength, and composition. Our results show that the investigated polyelectrolytes are usable as semi-permanent (physically adsorbed) coatings with at least five runs stability before a short coating regeneration is necessary. Both PECs showed a considerably decreased stability at pH 11.0. The EOF was higher using Good's buffers than with sodium phosphate buffer at the same pH and ionic strength. The thickness of the PEC layers studied by quartz crystal microbalance was 0.83 and 0.52 nm for PMOTAI and PIL-1, respectively. The hydrophobicity of the PEC layers was determined by analysis of a homologous series of alkyl benzoates and expressed as the distribution constants. Our result demonstrates that both PECs had comparable hydrophobicity, which enabled separation of compounds with log Po/w > 2. The ability to separate cationic drugs was shown with β-blockers, compounds often misused in doping. Both coatings were also able to separate hydrolysis products of the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-ene acetate at highly acidic conditions, where bare fused silica capillaries failed to accomplish the separation.

  9. Complex formation between polyelectrolytes and oppositely charged oligoelectrolytes

    Science.gov (United States)

    Zhou, Jiajia; Barz, Matthias; Schmid, Friederike

    2016-04-01

    We study the complex formation between one long polyanion chain and many short oligocation chains by computer simulations. We employ a coarse-grained bead-spring model for the polyelectrolyte chains and model explicitly the small salt ions. We systematically vary the concentration and the length of the oligocation and examine how the oligocations affects the chain conformation, the static structure factor, the radial and axial distribution of various charged species, and the number of bound ions in the complex. At low oligocation concentration, the polyanion has an extended structure. Upon increasing the oligocation concentration, the polyanion chain collapses and forms a compact globule, but the complex still carries a net negative charge. Once the total charge of the oligocations is equal to that of the polyanion, the collapse stops and is replaced by a slow expansion. In this regime, the net charge on the complexes is positive or neutral, depending on the microion concentration in solution. The expansion can be explained by the reduction of the oligocation bridging. We find that the behavior and the structure of the complex are largely independent of the length of oligocations, and very similar to that observed when replacing the oligocations by multivalent salt cations, and conclude that the main driving force keeping the complex together is the release of monovalent counterions and coions. We speculate on the implications of this finding for the problem of controlled oligolyte release and oligolyte substitution.

  10. Polyelectrolyte decomplexation via addition of salt: charge correlation driven zipper.

    Science.gov (United States)

    Antila, Hanne S; Sammalkorpi, Maria

    2014-03-20

    We report the first atomic scale studies of polyelectrolyte decomplexation. The complex between DNA and polylysine is shown to destabilize and spontaneously open in a gradual, reversible zipper-like mechanism driven by an increase in solution salt concentration. Divalent CaCl2 is significantly more effective than monovalent NaCl in destabilizing the complex due to charge correlations and water binding capability. The dissociation occurs accompanied by charge reversal in which charge correlations and ion binding chemistry play a key role. Our results are in agreement with experimental work on complex dissociation but in addition show the underlying microstructural correlations driving the behavior. Comparison of our full atomic level detail and dynamics results with theoretical works describing the PEs as charged, rigid rods reveals that although charge correlation involved theories provide qualitatively similar responses, considering also specific molecular chemistry and molecular level water contributions provides a more complete understanding of PE complex stability and dynamics. The findings may facilitate controlled release in gene delivery and more in general tuning of PE membrane permeability and mechanical characteristics through ionic strength.

  11. Lipid monolayers and adsorbed polyelectrolytes with different degrees of polymerization.

    Science.gov (United States)

    Ortmann, Thomas; Ahrens, Heiko; Lawrenz, Frank; Gröning, Andreas; Nestler, Peter; Günther, Jens-Uwe; Helm, Christiane A

    2014-06-17

    Polystyrene sulfonate (PSS) of different molecular weight M(w) is adsorbed to oppositely charged DODAB monolayers from dilute solutions (0.01 mmol/L). PSS adsorbs flatly in a lamellar manner, as is shown by X-ray reflectivity and grazing incidence diffraction (exception: PSS with M(w) below 7 kDa adsorbs flatly disordered to the liquid expanded phase). The surface coverage and the separation of the PSS chains are independent of PSS M(w). On monolayer compression, the surface charge density increases by a factor of 2, and the separation of the PSS chains decreases by the same factor. Isotherms show that on increase of PSS M(w) the transition pressure of the LE/LC (liquid expanded/liquid condensed) phase transition decreases. When the contour length exceeds the persistence length (21 nm), the transition pressure is low and constant. For low-M(w) PSS (<7 kDa) the LE/LC transition of the lipids and the disordered/ordered transition of adsorbed PSS occur simultaneously, leading to a maximum in the contour length dependence of the transition enthalpy. These findings show that lipid monolayers at the air/water interface are a suitable model substrate with adjustable surface charge density to study the equilibrium conformation of adsorbed polyelectrolytes as well as their interactions with a model membrane.

  12. STRUCTURAL SOLUTIONS AND SPECIAL FEATURES OF THE THERMAL PROTECTION ANALYSIS OF EXTERIOR WALLS OF BUILDINGS MADE OF AUTOCLAVED GAS-CONCRETE BLOCKS

    Directory of Open Access Journals (Sweden)

    Bedov Anatolij Ivanovich

    2012-10-01

    Full Text Available Relevant structural solutions, physical and mechanical characteristics, coefficients of thermal conductivity for exterior masonry walls made of autoclaved gas-concrete blocks are provided in the article. If a single-layer wall is under consideration, an autoclaved gas-concrete block is capable of performing the two principal functions of a shell structure, including the function of thermal protection and the bearing function. The functions are performed simultaneously. Therefore, the application of the above masonry material means the design development and erection of exterior walls of residential buildings noteworthy for their thermal efficiency. In the event of frameless structures, the height of the residential building in question may be up to 5 stories, while the use of a monolithic or a ready-made frame makes it possible to build high-rise buildings, and the number of stories is not limited in this case. If the average block density is equal to 400…500 kilograms per cubic meter, the designed wall thickness is to be equal to 400 mm. Its thermal resistance may be lower than the one set in the event of the per-element design of the thermal protection (Rreq = 3.41 м2 C/Watt, in Ufa, although it will meet the requirements of the applicable regulations if per-unit power consumption rate is considered.

  13. Micellar solutions of PEO-PPO-PEO block copolymers for in situ phenol removal from fermentation broth

    NARCIS (Netherlands)

    Heerema, L.D.; Cakali, D.; Roelands, C.P.M.; Goetheer, E.L.V.; Verdoes, D.; Keurentjes, J.

    2010-01-01

    The applicability of aqueous solutions of Pluronics for the removal of the model product phenol was evaluated. Phenol is a chemical that can be produced by a recombinant strain of the solvent tolerant bacterium Pseudomonas putida S12. However, the growth of the micro-organisms and the phenol

  14. Micellar solutions of PEO-PPO-PEO block copolymers for in situ phenol removal from fermentation broth

    NARCIS (Netherlands)

    Heerema, L.D.; Cakali, D.; Roelands, C.P.M.; Goetheer, E.L.V.; Verdoes, D.; Keurentjes, J.

    2010-01-01

    The applicability of aqueous solutions of Pluronics for the removal of the model product phenol was evaluated. Phenol is a chemical that can be produced by a recombinant strain of the solvent tolerant bacterium Pseudomonas putida S12. However, the growth of the micro-organisms and the phenol product

  15. Microstructure and Phase Behavior of Cationic Gemini/Anionic Polyelectrolyte/Water Ternary System

    Institute of Scientific and Technical Information of China (English)

    皮瑛瑛; 尚亚卓; 彭昌军; 刘洪来

    2006-01-01

    The microstructure of cationic gemini surfactant 1,6-bis(dodecyldimethylammonium) hexane dibromide [C12H25(CH3)2N-(CH2)6-N(CH3)2C12H25·2Br] (12-6-12·2Br-) and oppositely charged polyelectrolyte poly(acrylic acid,sodium salt) (NaPA) in aqueous solution has been studied by using fluorescence, conductivity measurement, freeze-etching and TEM. The data obtained from fluorescence and conductivity measurement show that micelle-like or complex can form between the gemini surfactant (12-6-12.2Br-) and polyelectrolyte NaPA due to the static electric interaction and hydrophobic forces. Through freeze-etching and TEM, the microstructure of the mixture solution has been studied, which is consistent with the result from micropolarity. Comparing the fluorescence spectrum of system of dodecyltrimethylammonium bromide (DTAB) and NaPA with that of system of gemini surfactant (12-6-12.2Br-) and NaPA, it can be found that the interaction of (12-6-12.2Br-) and NaPA in aqueous solution has also been detected. It can be shown that the precipitate will transform into gel in higher NaPA concentration.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hoffmann, Ingo, E-mail: ingo.hoffmann@tu-berlin.de [Stranski-Laboratorium für Physikalische und Theoretische Chemie, Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 124, Sekr. TC 7, D-10623 Berlin (Germany); Institut Max von Laue-Paul Langevin (ILL), F-38042 Grenoble Cedex 9 (France); Farago, Bela; Schweins, Ralf; Falus, Peter; Sharp, Melissa [Institut Max von Laue-Paul Langevin (ILL), F-38042 Grenoble Cedex 9 (France); Prévost, Sylvain [Stranski-Laboratorium für Physikalische und Theoretische Chemie, Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 124, Sekr. TC 7, D-10623 Berlin (Germany); Helmholtz-Zentrum Berlin, D-14109 Berlin (Germany); Gradzielski, Michael, E-mail: michael.gradzielski@tu-berlin.de [Stranski-Laboratorium für Physikalische und Theoretische Chemie, Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 124, Sekr. TC 7, D-10623 Berlin (Germany)

    2015-08-21

    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 different 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

  17. Adsorption of a synthetic heparinoid polyelectrolyte on an ion-exchanging surface

    NARCIS (Netherlands)

    Froehling, Peter E.; Bantjes, Adriaan; Kolar, Z.

    1977-01-01

    The adsorption of a synthetic heparinoid polyelectrolyte on poly(vinylchloride) previously treated with tridodecylmethylammonium chloride (TDMAC) was studied using radiotracer techniques to provide a more quantitative picture of antithrombogenic surface coatings. 125I-labeled polyelectrolyte was use

  18. Multilayered Polyelectrolyte Films:A Tool for Biomaterial Coatings and Tissue Engineering?

    Institute of Scientific and Technical Information of China (English)

    Jean-Claude; VOEGEL; Joёlle; OGIER; Catherine; PICART; Nadia; JESSEL; Philippe; LAVALLE; Vincent; BALL; Bernard; SENGER; Pierre; SCHAAF

    2005-01-01

    1 Physicochemical aspects of multilayered polyelectrolyte films Multilayered polyelectrolyte films are obtained by alternated depositions on a solid surface of polyanions and polycations~([1]). The driving force for the build-up results from the charge excess which appears on the top of the film after each new polyelectrolyte adsorption. The film top becomes thus positively (respectively negatively) charged when the film is ending by a polycation (respectively polyanion). Various polyelectrolyte systems hav...

  19. Complexation of oppositely charged polyelectrolytes in gene delivery and biology

    Science.gov (United States)

    Shklovskii, Boris

    2009-03-01

    Charge inversion of a DNA double helix by a positively charged flexible polymer (polyelectrolyte) is widely used to facilitate DNA contact with negative cell membranes for gene delivery. Motivated by this application in the first part of the talk I study the phase diagram a solution of long polyanions (PA) with a shorter polycations (PC) as a function the ratio of total charges of PC and PA in the solution, x, and the concentration of monovalent salt. Each PA attracts many PCs to form a complex. When x= 1, the complexes are neutral and condense in a macroscopic drop. When x is far away from 1, complexes are strongly charged and stable. PA are overcharged by PC at x > 1 and undercharged by PC at x vegetable viruses from long ss-RNA molecule paying role of scaffold and identical capsid proteins with long positive tails. I show that optimization Coulomb energy of the virus leads to the charge of RNA twice larger than the total charge of the capsid, in agreement with the experimental data. Then I discuss kinetics of the Coulomb complexation driven virus self-assembly. Capsid proteins stick to unassembled chain of ss RNA (which we call ``antenna'') and slide on it towards the assembly site. I show that at excess of capsid proteins such one-dimensional diffusion accelerates self-assembly more than ten times. On the other hand at excess of ss-RNA, antenna slows self-assembly down. Several experiments are proposed to verify the role of ss-RNA antenna in self-assembly.

  20. Insulin/poly(ethylene glycol)-block-poly(L-lysine) Complexes: Physicochemical Properties and Protein Encapsulation.

    Science.gov (United States)

    Pippa, Natassa; Kalinova, Radostina; Dimitrov, Ivaylo; Pispas, Stergios; Demetzos, Costas

    2015-06-04

    Insulin (INS) was encapsulated into complexes with poly(ethylene glycol)-block-poly(L-lysine) (PEG-b-PLys), which is a polypeptide-based block copolymer (a neutral-cationic block polyelectrolyte). The particular cationic-neutral block copolymer can complex INS molecules in aqueous media via electrostatic interactions. Light-scattering techniques are used to study the complexation process and structure of the hybrid nanoparticles in a series of buffers, as a function of protein concentration. The physicochemical and structural characteristics of the complexes depend on the ionic strength of the aqueous medium, while the concentration of PEG-b-PLys was constant through the series of solutions. As INS concentration increased the size distribution of the complexes decreased, especially at the highest ionic strength. The size/structure of complexes diluted in biological medium indicated that the copolymer imparts stealth properties and colloidal and biological stability to the complexes, features that could in turn affect the clearance properties in vivo. Therefore, these studies could be a rational roadmap for designing the optimum complexes/effective nanocarriers for proteins and peptides.

  1. Immobilization of hydrogenase on carbon nanotube polyelectrolytes as heterogeneous catalysts for electrocatalytic interconversion of protons and hydrogen

    Science.gov (United States)

    Liu, Jiang; Wu, Wen-Jie; Fang, Fang; Zorin, Nikolay A.; Chen, Meng; Qian, Dong-Jin

    2016-08-01

    Immobilization of active enzymes on the surfaces of electrodes and nanomaterials is important in the fields of bioscience, and biotechnology. In this study, we investigated electrocatalytic properties of the interconversion of protons and hydrogen by means of hydrogenase (H2ase)-functionalized carbon nanotube polyelectrolyte composites. Multiwalled carbon nanotube polyelectrolytes (MWNT-PEs) were synthesized through a diazonium and an addition reaction with poly(4-vinylpyridine) (P4VP), followed by another addition reaction with either methyl iodide (CH3I) or N-methyl- N'-benzyl bromide bipyridinium (VBenBr) to produce MWNT-P4VPMe or MWNT-P4VPBenV polyelectrolytes, respectively. The MWNT-PE@H2ase bio-nanocomposites were then prepared by means of MWNT-PEs as substrates to bind with H2ase. The redox current density of the MWNT-PE@H2ase-modified electrodes increased with a decrease in pH values of the Ar-saturated electrolyte solution owing to the catalytic reduction of protons (H2 production); further, it increased with the increasing pH values of the H2-saturated solution owing to the catalytic oxidation of hydrogen. The reversible color change between blue-colored and colorless viologen (catalyzed by the MWNT-PE@H2ase bio-nanocomposites) suggested that they may be developed as nano-biosensors for molecular H2. The as-synthesized bio-nanocomposites showed strong long-term stability and high bioactivity.

  2. Sustained, Controlled and Stimuli-Responsive Drug Release Systems Based on Nanoporous Anodic Alumina with Layer-by-Layer Polyelectrolyte

    Science.gov (United States)

    Porta-i-Batalla, Maria; Eckstein, Chris; Xifré-Pérez, Elisabet; Formentín, Pilar; Ferré-Borrull, J.; Marsal, Lluis F.

    2016-08-01

    Controlled drug delivery systems are an encouraging solution to some drug disadvantages such as reduced solubility, deprived biodistribution, tissue damage, fast breakdown of the drug, cytotoxicity, or side effects. Self-ordered nanoporous anodic alumina is an auspicious material for drug delivery due to its biocompatibility, stability, and controllable pore geometry. Its use in drug delivery applications has been explored in several fields, including therapeutic devices for bone and dental tissue engineering, coronary stent implants, and carriers for transplanted cells. In this work, we have created and analyzed a stimuli-responsive drug delivery system based on layer-by-layer pH-responsive polyelectrolyte and nanoporous anodic alumina. The results demonstrate that it is possible to control the drug release using a polyelectrolyte multilayer coating that will act as a gate.

  3. A COMPARATIVE STUDY OF CHAIN DYNAMICS OF DI-AND TRI-BLOCK COPOLYMERS IN SEMIDILUTE SOLUTION IN A NON-SELECTIVE SOLVENT

    Institute of Scientific and Technical Information of China (English)

    Wei Li; Liang-zhi Hong; To Ngai; Hai-ying Huang; Tian-bai He; Chi Wu

    2004-01-01

    The chain dynamics of a pair of diblock poly(styrene-b-butadiene) (PS210-b-PB960) and triblock poly(styrene-b-butadiene-b-styrene) (PS200-b-PB1815-b-PS200) copolymers in both dilute and semidilute toluene solutions has been comparatively studied by dynamic laser light scattering. As expected, the mutual diffusion of individual chain changes into a fast cooperative diffusion of the chain segments ("blobs") between two neighboring entanglement points for both the copolymers as the solution changes from dilute to semidilute. Further increases of the concentration lead to a second slow relaxation mode. For the triblock chains, there exists an additional middle relaxation between the fast and the slow modes.with 0.33 <α< 0.44, much smaller than 0.75 predicted or 0.72 observed for linear homopolymer chains in good solvent. It implies that the solvent quality of toluene for PB might not be as good as that for PS. Due to such a difference in solubility, it is reasonable to speculate that the PB and PS blocks are transiently segregated in semidilute solution. The relaxation of these transient PB and PS richer domains leads to the observed slow relaxation. Such a speculation is supported by the appearance of an additional slow relaxation mode in the study of polyisoprene-b-polystyrene-b-polyisoprene in semidilute solution in cyclohexane, a non-selective solvent, in which we alternated the solubility difference by a variation of the solution temperature.

  4. Protein adsorption in polyelectrolyte brush type cation-exchangers.

    Science.gov (United States)

    Khalaf, Rushd; Coquebert de Neuville, Bertrand; Morbidelli, Massimo

    2016-11-04

    Ion exchange chromatography materials functionalized with polyelectrolyte brushes (PEB) are becoming an integral part of many protein purification steps. Adsorption onto these materials is different than that onto traditional materials, due to the 3D partitioning of proteins into the polyelectrolyte brushes. Despite this mechanistic difference, many works have described the chromatographic behavior of proteins on polyelectrolyte brush type ion exchangers with much of the same methods as used for traditional materials. In this work, unconventional chromatographic behavior on polyelectrolyte brush type materials is observed for several proteins: the peaks shapes reveal first anti-Langmuirian and then Langmuirian types of interactions, with increasing injection volumes. An experimental and model based description of these materials is carried out in order to explain this behavior. The reason for this behavior is shown to be the 3D partitioning of proteins into the polyelectrolyte brushes: proteins that fully and readily utilize the 3D structure of the PEB phase during adsorption show this behavior, whereas those that do not show traditional ion exchange behavior.

  5. Coacervation in Symmetric Mixtures of Oppositely Charged Rodlike Polyelectrolytes

    Science.gov (United States)

    Kumar, Rajeev; Fredrickson, Glenn

    2010-03-01

    Phase separation in the salt-free symmetric mixtures of oppositely charged rodlike polyelectrolytes is studied using quasi-analytical calculations. Stability analyses for the isotropic-isotropic and the isotropic-nematic phase transitions in the symmetric mixtures are carried out. It is shown that electrostatics favor nematic ordering. Also, the coexistence curves for the symmetric mixtures are computed, and the effects of the linear charge density and the electrostatic interaction strength on the phase boundaries are studied. It is found that the counterions are uniformly distributed in the coexisting phases for low electrostatic interaction strengths characterized by the linear charge density of the polyelectrolytes and the Bjerrum's length. However, the counterions also phase separate along with the rodlike polyelectrolytes with an increase in the electrostatic interaction strength. It is shown that the number density of the counterions is higher in the concentrated (or coacervate) phase than in the dilute (or supernatant) phase. In contrast to the rodlike mixtures, flexible polyelectrolyte mixtures can undergo only isotropic-isotropic phase separation. A comparison of the coexistence curves for the weakly charged rodlike with the flexible polyelectrolyte mixtures reveals that the electrostatic driving force for the isotropic-isotropic phase separation is stronger in the flexible mixtures.

  6. Characteristics of model polyelectrolyte multilayer films containing laponite clay nanoparticles.

    Science.gov (United States)

    Elzbieciak, M; Wodka, D; Zapotoczny, S; Nowak, P; Warszynski, P

    2010-01-05

    Polyelectrolyte films structure formed by the "layer-by-layer" (LbL) technique can be enriched by addition of charged nanoparticles like carbon nanotubes and silver or hydroxyapatite nanoparticles, which can improve properties of the polyelectrolyte films or modify their functionality. In our paper we examined the formation and properties of model polyelectrolyte multilayers containing a synthetic layered silicate, Laponite. The Laponite nanoparticles were incorporated into multilayer films, which were formed from weak, branched polycation PEI and strong polyanion PSS. Since charge of PEI is pH-dependent, we build up multilayer films in two deposition conditions: pH = 6 when PEI was strongly charged and pH = 10.5 when charge density of PEI was low. Thicknesses of the films constructed with various numbers of Laponite layers were measured by single wavelength ellipsometry. We also determined the differences in permeability for selected electroactive molecules using cyclic voltamperometry. Properties of the films containing clay nanoparticles were compared with model polyelectrolyte multilayer films PEI/PSS formed at the same conditions. We found that Laponite nanoparticles strongly influenced PEI/PSS multilayer film properties. Replacement of PSS by Laponite eliminated the oscillations of the film thickness in the case when PEI was weakly charged. PSS layer adsorbed on top of PEI/Laponite bilayers increased the thickness of multilayer films and improved their barrier properties so synergistic effects between these properties for polyelectrolytes and Laponite nanoparticles could be observed.

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

    Science.gov (United States)

    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.

  8. A Solution-Processable Molecule using Thieno[3,2-b]thiophene as Building Block for Efficient Organic Solar Cells.

    Science.gov (United States)

    Wei, Huan; Chen, Weichao; Han, Liangliang; Wang, Ting; Bao, Xichang; Li, Xiaoyun; Liu, Jie; Zhou, Yuanhang; Yang, Renqiang

    2015-08-01

    A solution-processed acceptor-π-donor-π-acceptor (A-π-D-π-A) type small molecule, namely DCATT, has been designed and synthesized for the application as donor material in organic solar cells. The fused aromatic unit thieno[3,2-b]thiophene (TT) flanked with thiophene is applied as π bridge, while 4,8-bisthienyl substituted benzodithiophene (BDT) and 2-ethylhexyl cyanoacetate are chosen as the central building block and end group, respectively. Introduction of fused ring to the small molecule enhances the conjugation length of the main chain, and gives a strong tendency to form π-π stacking with a large overlapping area which favors to high charge carrier transport. Small-molecule organic solar cells based on blends of DCATT and fullerene acceptor exhibit power conversion efficiencies as high as 5.20 % under the illumination of AM 1.5G, 100 mW cm(-2) .

  9. Superhydrophilic Polyelectrolyte Brush Layers with Imparted Anti-Icing Properties

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Järn, Mikael; Shimizu, Kyoko;

    2014-01-01

    This work demonstrates the feasibility of superhydrophilic polyelectrolyte brush coatings for anti-icing applications. Five different types of ionic and nonionic polymer brush coatings of 25-100 nm thickness were formed on glass substrates using silane chemistry for surface premodification followed......(-), SO4(2-), and C12SO3(-) ions. By consecutive measurements of the strength of ice adhesion toward ion-incorporated polymer brushes on glass it was found that Li(+) ions reduce ice adhesion by 40% at -18 °C and 70% at -10 °C. Ag(+) ions reduce ice adhesion by 80% at -10 °C relative to unmodified glass....... In general, superhydrophilic polyelectrolyte brushes exhibit better anti-icing property at -10 °C compared to partially hydrophobic brushes such as poly(methyl methacrylate) and surfactant exchanged polyelectrolyte brushes. The data are interpreted using the concept of a quasi liquid layer (QLL...

  10. An electrochemical aptasensor for chiral peptide detection using layer-by-layer assembly of polyelectrolyte-methylene blue/polyelectrolyte-graphene multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Qin Haixia; Liu Jiyang; Chen Chaogui [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Wang Jiahi, E-mail: jhwang@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Wang Erkang, E-mail: ekwang@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

    2012-01-27

    Highlights: Black-Right-Pointing-Pointer An electrochemical aptasensor for selective detection of peptide is constructed. Black-Right-Pointing-Pointer This aptasensor is based on grapheme multilayer via layer-by-layer assembly. Black-Right-Pointing-Pointer Such multilayer facilitates electron transfer and provides more adsorption sites. - Abstract: Here we demonstrate for the first time that by physically adsorbing aptamer onto conductive film assembled via alternate adsorption of graphene/polyelectrolyte and methylene blue/polyelectrolyte, a label-free electrochemical aptasensor with high sensitivity and selectivity for peptide detection is constructed. Graphene multilayer derived from layer-by-layer assembly has played significant roles in this sensing strategy: allowing accumulation of methylene blue, facilitating electron transfer and providing much more adsorption site. As compared to previous electrochemical aptasensors, the current sensor based on graphene multilayer alternated with electroactive molecule layer offers extremely high capability for sensitive detection of target without interference of environmental surrounding. This electroactive probe-confined graphene multilayer confers great flexibility to combine with differential pulse voltammetry (DPV) together. In the presence of target D entiomer of arginine vasopressin (D-VP), the binding of peptide to aptamer block the electron transfer process of MB, leading to decreased current peak of DPV. By this way, this electrochemical aptasensor based on electroactive molecule-intercalated graphene multilayer provide highly sensitive and specific detection of D-VP with the lowest detectable concentration of 1 ng mL{sup -1} and a wide detection range from 1 to 265 ng mL{sup -1}.

  11. Multilayered polyelectrolyte microcapsules: interaction with the enzyme cytochrome C oxidase.

    Science.gov (United States)

    Pastorino, Laura; Dellacasa, Elena; Noor, Mohamed R; Soulimane, Tewfik; Bianchini, Paolo; D'Autilia, Francesca; Antipov, Alexei; Diaspro, Alberto; Tofail, Syed A M; Ruggiero, Carmelina

    2014-01-01

    Cell-sized polyelectrolyte capsules functionalized with a redox-driven proton pump protein were assembled for the first time. The interaction of polyelectrolyte microcapsules, fabricated by electrostatic layer-by-layer assembly, with cytochrome c oxidase molecules was investigated. We found that the cytochrome c oxidase retained its functionality, that the functionalized microcapsules interacting with cytochrome c oxidase were permeable and that the permeability characteristics of the microcapsule shell depend on the shell components. This work provides a significant input towards the fabrication of an integrated device made of biological components and based on specific biomolecular functions and properties.

  12. CONJUGATED POLYMERS AND POLYELECTROLYTES IN SOLAR PHOTOCONVERSION, Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Schanze, Kirk S [University of Florida

    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.

  13. Multilayered polyelectrolyte microcapsules: interaction with the enzyme cytochrome C oxidase.

    Directory of Open Access Journals (Sweden)

    Laura Pastorino

    Full Text Available Cell-sized polyelectrolyte capsules functionalized with a redox-driven proton pump protein were assembled for the first time. The interaction of polyelectrolyte microcapsules, fabricated by electrostatic layer-by-layer assembly, with cytochrome c oxidase molecules was investigated. We found that the cytochrome c oxidase retained its functionality, that the functionalized microcapsules interacting with cytochrome c oxidase were permeable and that the permeability characteristics of the microcapsule shell depend on the shell components. This work provides a significant input towards the fabrication of an integrated device made of biological components and based on specific biomolecular functions and properties.

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

    Science.gov (United States)

    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

  15. Solution-phase submonomer diversification of aza-dipeptide building blocks and their application in aza-peptide and aza-DKP synthesis.

    Science.gov (United States)

    Bourguet, Carine B; Proulx, Caroline; Klocek, Sophie; Sabatino, David; Lubell, William D

    2010-06-01

    Aza-peptides have been used as tools for studying SARs in programs aimed at drug discovery and chemical biology. Protected aza-dipeptides were synthesized by a solution-phase submonomer approach featuring alkylation of N-terminal benzophenone semicarbazone aza-Gly-Xaa dipeptides using different alkyl halides in the presence of potassium tert-butoxide as base. Benzophenone protected aza-dipeptide tert-butyl ester 31c was selectively deprotected at the C-terminal ester or N-terminal hydrazone to afford, respectively, aza-dipeptide acid and amine building blocks 36c and 40c, which were introduced into longer aza-peptides. Alternatively, removal of the benzophenone semicarbazone protection from aza-dipeptide methyl esters 29a-c led to intramolecular cyclization to produce aza-DKPs 39a-c. In light of the importance of aza-peptides and DKPs as therapeutic agents and probes of biological processes, this diversity-oriented solution-phase approach may provide useful tools for studying peptide science. (c) 2010 European Peptide Society and John Wiley & Sons, Ltd.

  16. Larger red-shift in optical emissions obtained from the thin films of globular proteins (BSA, lysozyme) - polyelectrolyte (PAA) complexes

    Science.gov (United States)

    Talukdar, Hrishikesh; Kundu, Sarathi; Basu, Saibal

    2016-09-01

    Globular proteins (lysozyme and BSA) and polyelectrolyte (sodium polyacrylic acid) are used to form protein-polyelectrolyte complexes (PPC). Out-of-plane structures of ≈30-60 nm thick PPC films and their surface morphologies have been studied by using X-ray reflectivity and atomic force microscopy, whereas optical behaviors of PPC and protein conformations have been studied by using UV-vis, photoluminescence and FTIR spectroscopy respectively. Our study reveals that thin films of PPC show a larger red-shift of 23 and 16 nm in the optical emissions in comparison to that of pure protein whereas bulk PPC show a small blue-shift of ≈3 nm. A small amount of peak-shift is found to occur due to the heat treatment or concentration variation of the polyelectrolyte/protein in bulk solution but cannot produce such film thickness independent larger red-shift. Position of the emission peak remains nearly unchanged with the film thickness. Mechanism for such larger red-shift has been proposed.

  17. STRUCTURE-PROPERTY RELATIONSHIP OF POLYELECTROLYTES AND ITS APPLICATION IN STABILIZING DRILLING-MUD IN PRESENCE OF SALTS

    Institute of Scientific and Technical Information of China (English)

    LI Zhuomei; ZHANG Xuexin; XIE Zhiming; HUANG Yuhui

    1990-01-01

    A new polyelectrolyte (SPU) has been prepared. It can depress the water-loss of drilling-mud much more effective than the commonly used acrylic polyelectrolytes even in 30% NaCl solution.SPU has phenyl group in the backbone with -SO3- in the side chain while the acrylic polyelectrolytes have C- C and -COO- respectively. there exists an intrinsic relationship between the structure of polymer and its tolerance to salts. It has been found: 1 ) The adsorption amount of polymer on clay is related closely to the flexibility of polymer chain. 2) The salt-tolerance of -SO3-is superior to -COO-. 3) Both SPU-mud and HPAN-mud are plastic fluids. The dependence of yield point on salts relates to the molecular weight of polymer and hydration of ionogenic group,which is quite different for SPU-mud and HPAN-mud. 4) The extent of raising zeta-potential of base-mud by SPU is greater than by HPAN, but the extent of dropping zeta-potential of SPU-mud by NaCl is smaller than HPAN-mud. According to these results we suppose the salt-tolerance of SPU-mud is attributed mainly to hydration of -SO3- and that of HPAN-mud mainly to network structure formed in the drilling-mud.

  18. Conjugated polyelectrolyte hole transport layer for inverted-type perovskite solar cells

    Science.gov (United States)

    Choi, Hyosung; Mai, Cheng-Kang; Kim, Hak-Beom; Jeong, Jaeki; Song, Seyeong; Bazan, Guillermo C.; Kim, Jin Young; Heeger, Alan J.

    2015-06-01

    Organic-inorganic hybrid perovskite materials offer the potential for realization of low-cost and flexible next-generation solar cells fabricated by low-temperature solution processing. Although efficiencies of perovskite solar cells have dramatically improved up to 19% within the past 5 years, there is still considerable room for further improvement in device efficiency and stability through development of novel materials and device architectures. Here we demonstrate that inverted-type perovskite solar cells with pH-neutral and low-temperature solution-processable conjugated polyelectrolyte as the hole transport layer (instead of acidic PEDOT:PSS) exhibit a device efficiency of over 12% and improved device stability in air. As an alternative to PEDOT:PSS, this work is the first report on the use of an organic hole transport material that enables the formation of uniform perovskite films with complete surface coverage and the demonstration of efficient, stable perovskite/fullerene planar heterojunction solar cells.

  19. The bulk phase behavior of short polyelectrolyte chains: A Monte Carlo study

    Science.gov (United States)

    Orkoulas, Gerassimos; Kumar, Sanat

    2002-03-01

    While polyelectrolytes form an important class of materials in chemistry and biochemistry, their understanding at the theoretical level is still lacking. The strong Coulombic repulsions and attractions, the resulting Debye screening and the concomitant unlike-charge association (known as counterion condensation) render standard neutral polymer theories difficult to apply. Indeed, most theoretical and numerical investigations have been focused on the dilute-to-semidilute regime at somewhat weak Coulomb couplings. In this work, we consider a lattice model of flexible charged chains with an appropriate number of oppositely charged counterions to ensure electrical neutrality. Electrostatic interactions are explicitly taken into account and handled via Ewald sums in the simulations. The solvent is modeled as a uniform dielectric continuum. By performing grand canonical Monte Carlo simulations, we demonstrate that at strong Coulomb couplings (low reduced temperatures) the system separates into polymer rich and poor phases respectively. The type of phase coexistence occurring in these polyelectrolyte systems bears resemblances to the gas-liquid transition of the restricted primitive model of ionic solutions. The approach to the Flory theta point is studied by increasing the chain length. The critical point dependence on the chain length is found to be rather weak. A plausible explanation lies in the formation of long-lived network structures via a bead-counterion mechanism. Finally, the ability of the system to form gels via bead-counterion junctions is examined and analyzed.

  20. Dielectric analysis based on spherical-shell model for cationic and anionic spherical polyelectrolyte brushes

    Science.gov (United States)

    Guo, Xiaoxia; Zhao, Kongshuang

    2017-07-01

    We report here a dielectric study on cationic and anionic spherical polyelectrolyte brush (SPB) (consisting of a polystyrene (PS) core and poly (2-aminoethylmethacrylate hydrochloride (PAEMH) chains or poly (acrylic acid) (PAA) chains grafted onto the core) suspensions over a frequency range of 40 Hz-110 MHz. The relaxation behavior of the suspensions shows significant changes in the brush layer properties when changing the particle mass fraction or pH of the system. After eliminating the electrode polarization effect at a low frequency, two definite relaxations related to interfacial polarization, around 100 kHz and 10 MHz respectively, are observed. Based on a single layer spherical-shell model, we developed a curve-fitting procedure to analyze such dielectric spectra for soft particles, and then calculated the dielectric properties of the components of the SPBs (such as the permittivities and conductivities of the layer and solution phase), especially the layer thickness d s of the polyelectrolyte chain (PE) layer. We also found a larger confinement degree of counterions in the PAEMH brush due to the protonation of the amino group. Moreover, the repulsive force between the SPB particles is evaluated by using the d s combined with the relative theoretical formulas. We conclude that by raising (reducing) the acidity of the system, the stability of the PAEMH-SPB (PAA-SPB) suspension was improved. An increase in particle concentration can also improve the stability of these two dispersions.

  1. Rock blocks

    OpenAIRE

    Turner, W.

    2007-01-01

    Consider representation theory associated to symmetric groups, or to Hecke algebras in type A, or to q-Schur algebras, or to finite general linear groups in non-describing characteristic. Rock blocks are certain combinatorially defined blocks appearing in such a representation theory, first observed by R. Rouquier. Rock blocks are much more symmetric than general blocks, and every block is derived equivalent to a Rock block. Motivated by a theorem of J. Chuang and R. Kessar in the case of sym...

  2. Polyelectrolytes Ability in Reducing Atrazine Concentration in Water: Surface Effects

    NARCIS (Netherlands)

    Mohd Amin, M.F.; Heijman, S.G.J.; Lopes, S.I.C.; Rietveld, L.C.

    2014-01-01

    This paper reports on the direct ability of two positively charged organic polyelectrolytes (natural-based and synthetic) to reduce the atrazine concentration in water. The adsorption study was set up using multiple glass vessels with different polymer dosing levels followed by ultrafiltration with

  3. Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

    Science.gov (United States)

    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).

  4. Polyelectrolyte stabilized multilayered liposomes for oral delivery of paclitaxel

    DEFF Research Database (Denmark)

    Jain, Sanyog; Kumar, Dinesh; Swarnakar, Nitin K

    2012-01-01

    Paclitaxel (PTX) loaded layersome formulations were prepared using layer-by-layer assembly of the polyelectrolytes over liposomes. Stearyl amine was utilized to provide positive charge to the liposomes, which were subsequently coated with anionic polymer polyacrylic acid (PAA) followed by coating...

  5. Salt-induced release of lipase from polyelectrolyte complex micelles

    NARCIS (Netherlands)

    Lindhoud, Saskia; de Vries, Renko; Schweins, Ralf; Stuart, Martien A. Cohen; Norde, Willem

    2009-01-01

    With the aim to gain insight into the possible applicability of protein-filled polyelectrolyte complex micelles under physiological salt conditions, we studied the behavior of these micelles as a function of salt concentration. The micelles form by electrostatically driven co-assembly from strong ca

  6. Polyelectrolyte microcapsules for sustained delivery of water-soluble drugs

    Energy Technology Data Exchange (ETDEWEB)

    Anandhakumar, S.; Debapriya, M. [Department of Materials Engineering, Indian Institute of Science, Bangalore, 560012 (India); Nagaraja, V. [Department of Microbiology and Cell Biology, Indian Institute of Science, Bangalore, 560012 (India); Raichur, Ashok M., E-mail: amr@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore, 560012 (India)

    2011-03-12

    Polyelectrolyte capsules composed of weak polyelectrolytes are introduced as a simple and efficient system for spontaneous encapsulation of low molecular weight water-soluble drugs. Polyelectrolyte capsules were prepared by layer-by-layer (LbL) assembling of weak polyelectrolytes, poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) on polystyrene sulfonate (PSS) doped CaCO{sub 3} particles followed by core removal with ethylene-diaminetetraacetic acid (EDTA). The loading process was observed by confocal laser scanning microscopy (CLSM) using tetramethylrhodamineisothiocyanate labeled dextran (TRITC-dextran) as a fluorescent probe. The intensity of fluorescent probe inside the capsule decreased with increase in cross-linking time. Ciprofloxacin hydrochloride (a model water-soluble drug) was spontaneously deposited into PAH/PMA capsules and their morphological changes were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The quantitative study of drug loading was also elucidated which showed that drug loading increased with initial drug concentration, but decreased with increase in pH. The loaded drug was released in a sustained manner for 6 h, which could be further extended by cross-linking the capsule wall. The released drug showed significant antibacterial activity against E. coli. These findings indicate that such capsules can be potential carriers for water-soluble drugs in sustained/controlled drug delivery applications.

  7. Humidity Sensitive Properties of a Silicone-containing Polyelectrolyte Material

    Institute of Scientific and Technical Information of China (English)

    Mu Jie YANG; Zong Wu YAO; You Si CHEN; Yang LI

    2006-01-01

    Resistive-type film humidity sensors were prepared with a silicone-containing polyelectrolyte (Si-PE) and their humidity sensitive properties have been investigated. The sensors so obtained show high sensitivity to humidity variation over a wide range of RH (20-96%).In addition, they exhibit high reversibility, quick response and well long-term stability.

  8. Electrostatics and charge regulation in polyelectrolyte multilayered assembly.

    Science.gov (United States)

    Cherstvy, Andrey G

    2014-05-01

    We examine the implications of electrostatic interactions on formation of polyelectrolyte multilayers, in application to field-effect based biosensors for label-free detection of charged macromolecules. We present a quantitative model to describe the experimental potentiometric observations and discuss its possibilities and limitations for detection of polyelectrolyte adsorption. We examine the influence of the ionic strength and pH on the sensor response upon polyelectrolyte layer-by-layer formation. The magnitude of potential oscillations on the sensor-electrolyte interface predicted upon repetitive adsorption charge-alternating polymers agrees satisfactorily with experimental results. The model accounts for different screening by mobile ions in electrolyte and inside tightly interdigitated multilayered structure. In particular, we show that sensors' potential oscillations are larger and more persistent at lower salt conditions, while they decay faster with the number of layers at higher salt conditions, in agreement with experiments. The effects of polyelectrolyte layer thickness, substrate potential, and charge regulation on the sensor surface triggered by layer-by-layer deposition are also analyzed.

  9. Polyelectrolytes Ability in Reducing Atrazine Concentration in Water: Surface Effects

    NARCIS (Netherlands)

    Mohd Amin, M.F.; Heijman, S.G.J.; Lopes, S.I.C.; Rietveld, L.C.

    2014-01-01

    This paper reports on the direct ability of two positively charged organic polyelectrolytes (natural-based and synthetic) to reduce the atrazine concentration in water. The adsorption study was set up using multiple glass vessels with different polymer dosing levels followed by ultrafiltration with

  10. Formation of surface-attached microstructured polyelectrolyte brushes

    Institute of Scientific and Technical Information of China (English)

    Hai Ning Zhang

    2008-01-01

    Surface-attached micropatterned polyelectrolyte brushes on planar solid surfaces are generated using free radical polymerization photo-initiated by self-assembled initiator monolayers. It is shown that the formed patterns can be either negative or positive with different patterning processes.

  11. Estudo das interações entre o complexo polieletrolítico trimetilquitosana/carboximetilcelulose e Cu+2, ácido húmico e atrazina em solução aquosa Study of the interactions between the polyelectrolyte complex trimethylchitosan/carboxymethylcellulose and Cu+2, humic acid and atrazine in aqueous solution

    Directory of Open Access Journals (Sweden)

    Sergio P. Campana-Filho

    2009-01-01

    Full Text Available The polyelectrolyte complex (PEC resulting from the reaction of sodium carboxymethylcellulose (CMC and N,N,N-trimethylchitosan hydrochloride (TMQ was prepared and then characterized by infrared spectroscopy and energy dispersive X rays analysis. The interactions involving the PEC and Cu2+ ions, humic acid and atrazine in aqueous medium were studied. From the adsorption isotherms the maximum amount adsorbed (Xmax was determined as 61 mg Cu2+/g PEC, 171 mg humic acid/g PEC and 5 mg atrazine/g PEC. The results show that the CMC/TMQ complex has a high affinity for the studied species, indicating its potential application to remove them from aqueous media.

  12. Polyelectrolyte multilayer coatings for the separation of proteins by capillary electrophoresis: Influence of polyelectrolyte nature and multilayer crosslinking.

    Science.gov (United States)

    Bekri, Samya; Leclercq, Laurent; Cottet, Hervé

    2015-06-19

    The present work aims at studying the influence of the nature of the polyelectrolytes used in successive multiple ionic polymers on the performances of protein separation in acetic acid volatile background electrolyte. A broad library of polyelectrolyte multilayers was compared on the basis of 9 different weak/strong polyanions and 8 different weak/strong polycations. More than 20 couples of different polyelectrolytes were investigated. The separation efficiencies (expressed as the N/l ratio, where N is the plate number and l is the capillary effective length) were systematically compared for the separation of a protein test mixture. The coating stability was evaluated by the relative standard deviation of the migration times. For weak polyelectrolyte multilayers, the influence of the polymer crosslinking on the coating stability and separation efficiency has been studied. Intra-day repeatability of 100 successive runs, and capillary-to-capillary reproducibility were tested on coatings of each category (crosslinked and non crosslinked). The main (not obvious) result rising from this study is that the nature of the polyanion constituting the multilayers is of primary importance for the performance in terms of separation efficiency and stability, even when the mulilayers finish with a polycation.

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

    Science.gov (United States)

    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.

  14. Nanostructure of polymer monolayer and polyelectrolyte brush at air/water interface by X-ray and neutron reflectometry

    CERN Document Server

    Matsuoka, H; Matsumoto, K

    2003-01-01

    The nanostructure of amphiphilic diblock copolymer monolayer on water was directly investigated by in situ X-ray and neutron reflectivity techniques. The diblock copolymer consists of polysilacyclobutane, which is very flexible, as a hydrophobic block and polymethacrylic acid, an anionic polymer, as a hydrophilic block. The polymers with shorter hydrophilic segment formed a very smooth and uniform monolayer with hydrophobic layer on water and dense hydrophilic layer under the water. But the longer hydrophilic segment polymer formed three-layered monolayer with polyelectrolyte brush in addition to hydrophobic and dense hydrophilic layers. The dense hydrophilic layer is thought to be formed to avoid a contact between hydrophobic polymer layer and water. Its role is something like a 'carpet'. An additional interesting information is that the thickness of the 'carpet layer' is almost 15A, independent the surface pressure and hydrophilic polymer length. Highly quantitative information was obtained about the nanost...

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

    Science.gov (United States)

    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 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

  16. Charge Inversion Effects in Electrophoresis of Polyelectrolytes in the Presence of Multivalent Counterions and Transversal Electric Fields

    Directory of Open Access Journals (Sweden)

    Sorin Nedelcu

    2014-12-01

    Full Text Available By molecular dynamics simulations we investigate the transport of charged polymers in confinement, under externally applied electric fields, in straight cylinders of uniform diameter and in the presence of monovalent or multivalent counterions. The applied electric field has two components; a longitudinal component along the axis of the cylinder and a transversal component perpendicular to the cylinder axis. The direction of electrophoretic velocity depends on the polyelectrolyte length, valency of the counterions present in solution and transversal electric field value. A statistical model is put forward in order to explain these observations.

  17. pH-regulated ionic current rectification in conical nanopores functionalized with polyelectrolyte brushes.

    Science.gov (United States)

    Zeng, Zhenping; Ai, Ye; Qian, Shizhi

    2014-02-14

    Mimicking biological ion channels capable of pH-regulated ionic transport, synthetic nanopores functionalized with pH-tunable polyelectrolyte (PE) brushes have been considered as versatile tools for active transport control of ions, fluids, and bioparticles on the nanoscale. The ionic current rectification (ICR) phenomenon through a conical nanopore functionalized with PE brushes whose charge highly depends upon the local solution properties (i.e., pH and background salt concentration) is studied theoretically for the first time. The results show that the rectification magnitude, as well as the preferential rectification direction, is sensitive to the pH stimulus. The bulk concentration of the background salt can also significantly influence the charge of the PE brushes and accordingly affect the ICR phenomenon. The obtained results provide an insightful understanding of the pH-regulated ICR and guidelines for designing nanopores functionalized with PE brushes for pH-tunable applications.

  18. Highly Conductive Graphene and Polyelectrolyte Multilayer Thin Films Produced From Aqueous Suspension.

    Science.gov (United States)

    Stevens, Bart; Guin, Tyler; Sarwar, Owais; John, Alyssa; Paton, Keith R; Coleman, Jonathan N; Grunlan, Jaime C

    2016-09-27

    Rapid, large-scale exfoliation of graphene in water has expanded its potential for use outside niche applications. This work focuses on utilizing aqueous graphene dispersions to form thin films using layer-by-layer processing, which is an effective method to produce large-area coatings from water-based solutions of polyelectrolytes. When layered with polyethyleneimine, graphene flakes stabilized with cholate are shown to be capable of producing films thinner than 100 nm. High surface coverage of graphene flakes results in electrical conductivity up to 5500 S m(-1) . With the relative ease of processing, the safe, cost effective nature of the ingredients, and the scalability of the deposition method, this system should be industrially attractive for producing thin conductive films for a variety of electronic and antistatic applications.

  19. Self-assembled systems of water soluble metal 8-hydroxyquinolates with surfactants and conjugated polyelectrolytes

    DEFF Research Database (Denmark)

    Burrows, Hugh D.; Costa, Telma; Luisa Ramos, M.

    2016-01-01

    We have studied the interaction of 8-hydroxyquinoline-5-sulfonate (8-HQS) with the metal ions Al(III) and Zn(II) in aqueous solution in the presence of tetraalkylammonium surfactants using UV/vis absorption, fluorescence, NMR spectroscopy and electrical conductivity measurements, complemented by ...... assembly between the conjugated polyelectrolyte and the metal/8-HQS complex, as demonstrated by electronic energy transfer. The potential of these systems in sensing, light harvesting, and electron injection/transport layers in organic semiconductor devices is discussed....... by DFT calculations and molecular dynamics (MD) simulations. Under appropriate conditions, complexes between 8-HQS and metal ions form rapidly, and have similar electronic, spectroscopic and photophysical properties to the corresponding metal quinolates, such as Alq3. These interact with the cationic...

  20. Multifunctional polyelectrolyte microcapsules as a contrast agent for photoacoustic imaging in blood.

    Science.gov (United States)

    Yashchenok, Alexey M; Jose, Jithin; Trochet, Philippe; Sukhorukov, Gleb B; Gorin, Dmitry A

    2016-08-01

    The polyelectrolyte microcapsules that can be accurate either visualized in biological media or in tissue would enhance their further in vivo application both as a carrier of active payloads and as a specific sensor. The immobilization of active species, for instance fluorescent dyes, quantum dots, metal nanoparticles, in polymeric shell enables visualization of capsules by optical imaging techniques in aqueous solution. However, for visualization of capsules in complex media an instrument with high contrast modality requires. Herein, we show for the first time photoacoustic imaging (PAI) of multifunctional microcapsules in water and in blood. The microcapsules exhibit greater photoacoustic intensity compare to microparticles with the same composition of polymeric shell presumably their higher thermal expansion. Photoacoustic intensity form microcapsules dispersed in blood displays an enhancement (2-fold) of signal compare to blood. Photoacoustic imaging of microcapsules might contribute to non-invasive carrier visualization and further their in vivo distribution.

  1. Proton conducting gel polyelectrolytes based on 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Zygadlo-Monikowska, Ewa; Florjanczyk, Zbigniew; Wielgus-Barry, Edyta; Hildebrand, Ewa [Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, 00-664 Warszawa (Poland)

    2006-09-13

    Polyelectrolytes of 2-acrylamido-2-methyl-propanesulfonic acid (AMPSA) in the form of crosslinked hydrogels have been obtained. The effect of the amount of crosslinking agent, N,N'-methylene-bis-acrylamide (BAA), and water content on the conductivity and mechanical properties of the gels obtained was studied and the results were compared with those of poly(AMPSA) aqueous solutions. The highest {sigma} values, of the order of 1Scm{sup -1} are reached by systems containing 60-80wt.% of water and 1-2wt.% BAA. These systems form flexible and transparent membranes. Modification of the mechanical properties of hydrogels consisting in the synthesis of structures of mutually interpenetrating polymer networks of poly(vinylidene fluoride) and poly(vinyl alcohol) (PVA) was performed. The thermal properties of these modified gels were studied. (author)

  2. Polysaccharide-based polyelectrolytes hollow microcapsules constructed by layer-by-layer technique.

    Science.gov (United States)

    Zhang, Yifeng; Chen, Cong; Wang, Jianguo; Zhang, Lina

    2013-07-25

    Two water-soluble polysaccharide derivatives, carboxymethylated and quarternized glucans (CMGP and QGP) were synthesized for the first time from water-insoluble polysaccharides (GP) extracted from Ganoderma lucidum. Hollow microspheres were constructed using electrostatic layer-by-layer (LbL) deposition of the CMGP and QGP polyelectrolytes onto colloidal ZnO particles followed by the core decomposition with an acid solution. The structures of the multilayered CMGP/QGP microspheres were investigated by transmission electron microscopy (TEM), zeta potential and dynamic light scattering (DLS). The results revealed that the multilayer thickness increased regularly from 48 to 145 nm as the number of deposited CMGP/QGP layers was increased from two to seven, and the mean increment of thickness was ∼25 nm per layer, reflecting the high regularity of the layer-by-layer assembly. This work provided an easy method to construct hollow microcapsules with biocompatibility and controlled dimensions.

  3. Layer-by-layer deposition of oppositely charged polyelectrolytes on the surface of condensed DNA particles.

    Science.gov (United States)

    Trubetskoy, V S; Loomis, A; Hagstrom, J E; Budker, V G; Wolff, J A

    1999-08-01

    DNA can be condensed with an excess of poly-cations in aqueous solutions forming stable particles of submicron size with positive surface charge. This charge surplus can be used to deposit alternating layers of polyanions and polycations on the surface surrounding the core of condensed DNA. Using poly-L-lysine (PLL) and succinylated PLL (SPLL) as polycation and polyanion, respectively, we demonstrated layer-by-layer architecture of the particles. Polyanions with a shorter carboxyl/backbone distance tend to disassemble binary DNA/PLL complexes by displacing DNA while polyanions with a longer carboxyl/backbone distance effectively formed a tertiary complex. The zeta potential of such complexes became negative, indicating effective surface recharging. The charge stoichiometry of the DNA/PLL/SPLL complex was found to be close to 1:1:1, resembling poly-electrolyte complexes layered on macrosurfaces. Recharged particles containing condensed plasmid DNA may find applications as non-viral gene delivery vectors.

  4. On the scattering properties of polyelectrolyte gels

    Science.gov (United States)

    Barrat, Jean-Louis; Joanny, Jean-François; Pincus, Phil

    1992-08-01

    We present a simple model for scattering properties of polyelectrolyte gels at swelling equilibrium. In the weak screening limit where the Debye-Hückel screening length is larger than the mesh size of the gel, the direct electrostatic interactions are negligible and the swelling is driven by the osmotic pressure of the counterions. The tension created by this pressure is transmitted through the crosslinks to the elastic chains which behave as isolated chains with an applied force at their end points. The structure factor of the gel can be split into a frozen component due to the average concentration heterogeneities and a thermodynamic component due to concentration fluctuations. The frozen component has a peak at a wavevector of the order of the mesh size of the gel, the thermodynamic component has a peak at a higher wavevector of the order of the inverse transverse radius of the chains. At infinite times the dynamic structure factor relaxes towards the frozen component of the static structure factor. In the limit of small wavevectors the relaxation is diffusive with a diffusion constant equal to the Stokes diffusion constant of the Pincus blobs of the stretched chains. The diffusion constant shows a minimum at a wavevector of the order of the inverse transverse radius of the chains. Nous présentons un modèle simple pour étudier la diffusion de rayonnement par des gels polylectrolytes à l'équilibre de gonflement. Dans la limite d'écrantage faible où la longueur d'écran de Debye-Hückel est plus grande que la maille du gel, les interactions électrostatiques directes sont négligeables et le gonflement est dû à la pression osmotique des contreions. La tension créée par cette pression est transmise par les noeuds du gel aux chaines élastiques qui se comportent comme des chaines isolées avec une force extérieure appliquée aux extrémités. Le facteur de structure du gel est la somme d'une composante gelée due aux hétérogénéités de concentration

  5. SOLUTIONING

    Directory of Open Access Journals (Sweden)

    Maria de Hoyos Guajardo, Ph.D. Candidate, M.Sc., B.Eng.

    2004-11-01

    Full Text Available The theory that is presented below aims to conceptualise how a group of undergraduate students tackle non-routine mathematical problems during a problem-solving course. The aim of the course is to allow students to experience mathematics as a creative process and to reflect on their own experience. During the course, students are required to produce a written ‘rubric’ of their work, i.e., to document their thoughts as they occur as well as their emotionsduring the process. These ‘rubrics’ were used as the main source of data.Students’ problem-solving processes can be explained as a three-stage process that has been called ‘solutioning’. This process is presented in the six sections below. The first three refer to a common area of concern that can be called‘generating knowledge’. In this way, generating knowledge also includes issues related to ‘key ideas’ and ‘gaining understanding’. The third and the fourth sections refer to ‘generating’ and ‘validating a solution’, respectively. Finally, once solutions are generated and validated, students usually try to improve them further before presenting them as final results. Thus, the last section deals with‘improving a solution’. Although not all students go through all of the stages, it may be said that ‘solutioning’ considers students’ main concerns as they tackle non-routine mathematical problems.

  6. Polyelectrolyte complexes : Preparation, characterization, and use for control of wet and dry adhesion between surfaces

    OpenAIRE

    Ankerfors, Caroline

    2012-01-01

    This thesis examines polyelectrolyte complex (PEC) preparation, adsorption behaviour, and potential use for control of wet and dry adhesion between surfaces. PEC formation was studied using a jet-mixing method not previously used for mixing polyelectrolytes. The PECs were formed using various mixing times, and the results were compared with those for PECs formed using the conventional polyelectrolyte titration method. The results indicated that using the jet mixer allowed the size of the form...

  7. Optimisation of the self-assembly process: production of stable, alginate-based polyelectrolyte nanocomplexes with protamine

    Science.gov (United States)

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

    2017-06-01

    The aim of this work was to investigate the possibility of covalent cross-linker-free, polyelectrolyte complex formation at the nanoscale between alginic acid (as sodium alginate, ALG) and protamine (PROT). Optimisation of the self-assembly conditions was performed by varying the type of polymer used, pH of component solutions, mass mixing ratio of the components and the speed and order of component addition on the properties of complexes. Homogenous particles with nanometric sizes resulted when an aqueous dispersion of ALG was rapidly mixed with a solution of PROT. The polyelectrolyte complex between ALG and PROT was confirmed by infrared spectroscopy. To facilitate incorporation of drugs soluble at low pH, pH of ALG dispersion was decreased to 2; however, no nanoparticles (NPs) were formed upon complexation with PROT. Adjusting pH of PROT solution to 3 resulted in the formation of cationic or anionic NPs with a size range 70-300 nm. Colloidal stability of selected alginic acid low/PROT formulations was determined upon storage at room temperature and in liquid media at various pH. Physical stability of NPs correlated with the initial surface charge of particles and was time- and pH-dependent. Generally, better stability was observed for anionic NPs stored as native dispersions and in liquids covering a range of pH.

  8. Comprehensive and Systematic Analysis of the Immunocompatibility of Polyelectrolyte Capsules.

    Science.gov (United States)

    Zyuzin, Mikhail V; Díez, Paula; Goldsmith, Meir; Carregal-Romero, Susana; Teodosio, Cristina; Rejman, Joanna; Feliu, Neus; Escudero, Alberto; Almendral, María Jesús; Linne, Uwe; Peer, Dan; Fuentes, Manuel; Parak, Wolfgang J

    2017-02-15

    The immunocompability of polyelectrolyte capsules synthesized by layer-by-layer deposition has been investigated. Capsules of different architecture and composed of either non-degradable or biodegradable polymers, with either positively or negatively charged outer surface, and with micrometer size, have been used, and the capsule uptake by different cell lines has been studied and quantified. Immunocompatibility studies were performed with peripheral blood mononuclear cells (PBMCs). Data demonstrate that incubation with capsules, at concentrations relevant for practical applications, did not result in a reduced viability of cells, as it did not show an increased apoptosis. Presence of capsules also did not result in an increased expression of TNF-α, as detected with antibody staining, as well as at mRNA level. It also did not result in increased expression of IL-6, as detected at mRNA level. These results indicate that the polyelectrolyte capsules used in this study are immunocompatible.

  9. Fibrillar films obtained from sodium soap fibers and polyelectrolyte multilayers.

    Science.gov (United States)

    Zawko, Scott A; Schmidt, Christine E

    2011-08-01

    An objective of tissue engineering is to create synthetic polymer scaffolds with a fibrillar microstructure similar to the extracellular matrix. Here, we present a novel method for creating polymer fibers using the layer-by-layer method and sacrificial templates composed of sodium soap fibers. Soap fibers were prepared from neutralized fatty acids using a sodium chloride crystal dissolution method. Polyelectrolyte multilayers (PEMs) of polystyrene sulfonate and polyallylamine hydrochloride were deposited onto the soap fibers, crosslinked with glutaraldehyde, and then the soap fibers were leached with warm water and ethanol. The morphology of the resulting PEM structures was a dense network of fibers surrounded by a nonfibrillar matrix. Microscopy revealed that the PEM fibers were solid structures, presumably composed of polyelectrolytes complexed with residual fatty acids. These fibrillar PEM films were found to support the attachment of human dermal fibroblasts.

  10. Polyelectrolyte Multilayers in Microfluidic Systems for Biological Applications

    Directory of Open Access Journals (Sweden)

    Saugandhika Minnikanti

    2014-07-01

    Full Text Available The formation of polyelectrolyte multilayers (PEMs for the first time, two decades ago, demonstrating the assembly on charged substrates in a very simple and efficient way, has proven to be a reliable method to obtain structures tunable at the nanometer scale. Much effort has been put into the assembly of these structures for their use in biological applications. A number of these efforts have been in combination with microfluidic systems, which add to the nanoassembly that is already possible with polyelectrolytes, a new dimension in the construction of valuable structures, some of them not possible with conventional systems. This review focuses on the advancements demonstrated by the combination of PEMs and microfluidic systems, and their use in biological applications.

  11. Determination of three characteristic regimes of weakly charged polyelectrolytes monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, Farhan [Department of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Shin, Kwanwoo [Department of Chemistry and Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742 (Korea, Republic of)], E-mail: kshin@sogang.ac.kr; Choi, Jae-Hak [Advanced Radiation Technology Institute, KAERI, Jeongeup 580-185 (Korea, Republic of); Satija, Sushil K. [National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Kim, Joon-Seop [Department of Polymer Science and Engineering, Chosun University (Korea, Republic of); Rafailovich, Miriam H.; Sokolov, Jon [Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794 (United States)

    2008-09-15

    We have demonstrated that monolayer films of randomly charged polystyrene sulfonated acid (PSSA) can be produced by the Langmuir technique, and observed the micro-domain structures, produced by the phase separation of electrostatically charged moieties and the hydrophobic moieties. Using atomic force microscopy and Langmuir isotherm, we found three specific regimes for the polyelectrolytes with various degrees of sulfonation (4-35%); very low charged PSSA (4-5%) in the hydrophobic regime, moderately charged PSSA (6-16%) which possessed a well-balanced nature between electrostatic and the hydrophobic interactions, and strongly amphiphilic nature of PSSA (6-16%) in the ionomer regime. Finally, we could categorize PSSA 35% in the polyelectrolyte regime, due to the dominance of the electrostatic interactions over the hydrophobic interactions.

  12. Ultramicroelectrode studies of oxygen reduction in polyelectrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

    1997-12-31

    A study on the oxygen reduction reaction in a solid state electrochemical cell was presented. The oxygen reduction reaction is a rate limiting reaction in the operation of solid polymer electrolyte fuel cells which use H{sub 2} and O{sub 2}. Interest in the oxygen reduction reaction of platinum electrodes in contact with Nafion electrolytes stems from its role in fuel cell technology. The kinetics of the oxygen reduction reaction in different polyelectrolyte membranes, such as Nafion and non-Nafion membranes, were compared. The electrode kinetics and mass transport parameters of the oxygen reduction reaction in polyelectrolyte membranes were measured by ultramicroelectrode techniques. The major difference found between these two classes of membrane was the percentage of water, which is suggestive of superior electrochemical mass transport properties of the non-Nafion membranes. 2 refs. 1 fig.

  13. Fracturing fluid cleanup by controlled release of enzymes from polyelectrolyte complex nanoparticles

    Science.gov (United States)

    Barati Ghahfarokhi, Reza

    Guar-based polymer gels are used in the oil and gas industry to viscosify fluids used in hydraulic fracturing of production wells, in order to reduce leak-off of fluids and pressure, and improve the transport of proppants. After fracturing, the gel and associated filter cake must be degraded to very low viscosities using breakers to recover the hydraulic conductivity of the well. Enzymes are widely used to achieve this but injecting high concentrations of enzyme may result in premature degradation, or failure to gel; denaturation of enzymes at alkaline pH and high temperature conditions can also limit their applicability. In this study, application of polyelectrolyte nanoparticles for entrapping, carrying, releasing and protecting enzymes for fracturing fluids was examined. The objective of this research is to develop nano-sized carriers capable of carrying the enzymes to the filter cake, delaying the release of enzyme and protecting the enzyme against pH and temperature conditions inhospitable to native enzyme. Polyethylenimine-dextran sulfate (PEI-DS) polyelectrolyte complexes (PECs) were used to entrap two enzymes commonly used in the oil industry in order to obtain delayed release and to protect the enzyme from conditions inhospitable to native enzyme. Stability and reproducibility of PEC nanoparticles was assured over time. An activity measurement method was used to measure the entrapment efficiency of enzyme using PEC nanoparticles. This method was confirmed using a concentration measurement method (SDS-PAGE). Entrapment efficiencies of pectinase and a commercial high-temperature enzyme mixture in polyelectrolyte complex nanoparticles were maximized. Degradation, as revealed by reduction in viscoelastic moduli of borate-crosslinked hydroxypropyl guar (HPG) gel by commercial enzyme loaded in polyelectrolyte nanoparticles, was delayed, compared to equivalent systems where the enzyme mixture was not entrapped. This indicates that PEC nanoparticles delay the

  14. Population Blocks.

    Science.gov (United States)

    Smith, Martin H.

    1992-01-01

    Describes an educational game called "Population Blocks" that is designed to illustrate the concept of exponential growth of the human population and some potential effects of overpopulation. The game material consists of wooden blocks; 18 blocks are painted green (representing land), 7 are painted blue (representing water); and the remaining…

  15. Population Blocks.

    Science.gov (United States)

    Smith, Martin H.

    1992-01-01

    Describes an educational game called "Population Blocks" that is designed to illustrate the concept of exponential growth of the human population and some potential effects of overpopulation. The game material consists of wooden blocks; 18 blocks are painted green (representing land), 7 are painted blue (representing water); and the remaining…

  16. Complex Coacervation composed of Polyelectrolytes Alginate and Chitosan

    Institute of Scientific and Technical Information of China (English)

    盛楠楠

    2016-01-01

    Alginate sodium (ALG) and chitosan (CHI) can form fiber, films, microspheres, hydrogels and all with a wide range of biomedical applications.Few works have been done as a result of the easily flocculation of chitosan in negatively charged matrix.Complex coacervation composed of polyelectrolytes alginate and chitosan were successfully fabricated.The results showed that the lower molecular weights of the chitosan is better for the fabricated of the complex coacervation.

  17. Formation of polyelectrolyte multilayers: ionic strengths and growth regimes

    NARCIS (Netherlands)

    Tang, K.; Besseling, N.A.M.

    2015-01-01

    This article presents a study of layer-by-layer (LbL) formation of poly-electrolyte multilayers (PEMs). Upon increasing ionic strength LbL growth patterns vary from linear for the lowest salt concentrations ([NaCl] = 0, 0.001, and 0.01 M) to exponential (for [NaCl] = 0.5 and 1 M). The slope of the

  18. Polyelectrolyte Biomaterial Interactions Provide Nanoparticulate Carrier for Oral Insulin Delivery

    OpenAIRE

    Reis, Catarina Pinto; Ribeiro, António J; Veiga, Francisco; Neufeld, Ronald J; Damgé, Christiane

    2008-01-01

    Nanospheres are being developed for the oral delivery of peptide-based drugs such as insulin. Mucoadhesive, biodegradable, biocompatible, and acid-protective biomaterials are described using a combination of natural polyelectrolytes, with particles formulated through nanoemulsion dispersion followed by triggered in situgel complexation. Biomaterials meeting these criteria include alginate, dextran, chitosan, and albumin in which alginate/dextran forms the core matrix complexed with chitosan a...

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

    Science.gov (United States)

    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.

  20. Formation of polyelectrolyte multilayers: ionic strengths and growth regimes

    NARCIS (Netherlands)

    Tang, K.; Besseling, N.A.M.

    2015-01-01

    This article presents a study of layer-by-layer (LbL) formation of poly-electrolyte multilayers (PEMs). Upon increasing ionic strength LbL growth patterns vary from linear for the lowest salt concentrations ([NaCl] = 0, 0.001, and 0.01 M) to exponential (for [NaCl] = 0.5 and 1 M). The slope of the l

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

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Swati; Kundagrami, Arindam, E-mail: arindam@iiserkol.ac.in [Department of Physical Sciences, Indian Institute of Science Education and Research, Kolkata, Mohanpur 741246, West Bengal (India)

    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.

  2. The Effect of Temperature Treatment on the Structure of Polyelectrolyte Multilayers

    Directory of Open Access Journals (Sweden)

    Maximilian Zerball

    2016-04-01

    Full Text Available The study addresses the effect of thermal treatment on the internal structure of polyelectrolyte multilayers (PEMs. In order to get insight into the internal structure of PEMs, Neutron Reflectometry (NR was used. PEMs with a deuterated inner block towards the substrate and a non-deuterated outer block were prepared and measured in 1% RH and in D2O before and after a thermal treatment. Complementarily, PEMs with the same number of layers but completely non-deuterated were investigated by ellipsometry. The analysis for the overall thickness (d, the average scattering length density (SLD and the refractive index (n indicate a degradation of the PEM. The loss in material is independent of the number of layers, i.e., only a constant part of the PEM is affected by degradation. The analysis of the internal structure revealed a more complex influence of thermal treatment on PEM structure. Only the outermost part of the PEM degenerates, while the inner part becomes denser during the thermal treatment. In addition, the swelling behavior of PEMs is influenced by the thermal treatment. The untreated PEM shows a well pronounced odd—even effect, i.e., PDADMAC-terminated PEMs take up more water than PSS-terminated PEMs. After the thermal treatment, the odd-even effect becomes much weaker.

  3. Hollow polyelectrolyte multilayer tubes: mechanical properties and shape changes.

    Science.gov (United States)

    Mueller, Renate; Daehne, Lars; Fery, Andreas

    2007-07-26

    In this paper, novel hollow polyelectrolyte multilayer tubes from poly(diallyldimethylammonium chloride) (PDADMAC), poly(styrene sulfonate) (PSS), and poly(allylamine hydrochloride) (PAH) were prepared: Readily available glass fiber templates are coated with polyelectrolytes using the layer-by-layer technique, followed by subsequent fiber dissolution. Depending on the composition of the polymeric multilayer, stable hollow tubes or tubes showing a pearling instability are observed. This instability corresponds to the Rayleigh instability and is a consequence of an increased mobility of the polyelectrolyte chains within the multilayer. The well-defined stable tubes were characterized with fluorescence microscopy, confocal laser scanning microscopy, and atomic force microscopy (AFM). The tubes were found to be remarkably free of defects, which results in an impermeable tube wall for even low molecular weight molecules. The mechanical properties of the tubes were determined with AFM force spectroscopy in water, and because continuum mechanical models apply, the Young's modulus of the wall material was determined. Additionally, scaling relations for the dependency of tube stiffness on diameter and wall thickness were validated. Because both parameters can be experimentally controlled by our approach, the deformability of the tubes can be varied over a broad range and adjusted for the particular needs.

  4. Deflocculation of Cellulosic Suspensions with Anionic High Molecular Weight Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Markus Heikki Juhani Korhonen

    2014-04-01

    Full Text Available Pulp fibers have a strong tendency to form flocs in water suspensions, which may cause their undesirable distribution in the paper sheets. This flocculation can be controlled by adding, e.g., an anionic high molecular weight polyelectrolyte in the fiber suspension. The objective of this study was to investigate the effect of anionic polyelectrolytes on deflocculation kinetics, dewatering, and rheology of cellulosic suspensions. The results showed that both microfibrillated cellulose (MFC and macroscopic pulp fibers can be dispersed using anionic polyacrylamides (APAM. The higher the molecular weight of APAM, the higher is its effect. Adsorption experiments illustrate that anionic polyelectrolytes do not strongly attach to cellulose surfaces but they can be partly entrapped or can disperse nanocellulose fibrils (increase the swelling. Based on rheological experiments, the MFC network became weaker with APAM addition. Similar to the flocculation mechanism of cellulosic materials with polymers, deflocculation is also time dependent. Deflocculation occurs very rapidly, and the maximum deflocculation level is achieved within a few seconds. When mixing is continued, the floc size starts to increase again. Also dewatering was found to be strongly dependent on the contact time with the APAMs. These results indicate that the positive effects of anionic deflocculants are quickly diminished due to shear forces, and therefore, the best deflocculating effect is achieved using as short a contact time as possible.

  5. Tunable protein-resistance of polycation-terminated polyelectrolyte multilayers.

    Science.gov (United States)

    Tristán, Ferdinando; Palestino, Gabriela; Menchaca, J-Luis; Pérez, Elías; Atmani, Hassan; Cuisinier, Frédéric; Ladam, Guy

    2009-08-10

    The prevention of nonspecific protein adsorption is a crucial prerequisite for many biomedical and biotechnological applications. Therefore, the design of robust and versatile methods conferring optimal protein-resistance properties to surfaces has become a challenging issue. Here we report the unexpected case of polycation-ending polyelectrolyte multilayers (PEM) that efficiently prevented the adsorption of a negatively charged model protein, glucose oxidase (GOX). PEM films were based on two typical weak poyelectrolytes: poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA). No chemical modification of the polyelectrolytes was required and tunable GOX adsorption was possible by simply changing the buildup pH conditions. Protein-resistance properties are attributed to high film hydration becoming the predominant factor over electrostatic interactions. We explain this effect by oscillations of the internal PAA ionization state throughout the buildup, which results in an excess of carboxylic acid groups within the film. This excess acts as a reservoir of potential carboxylate groups compensating the outer PAH positive charges. Partial results indicated that the system was also resistant to the adsorption of a positively charged protein, lysozyme. Control of the internal ionization of weak polyelectrolyte multilayers might open a route toward simple tuning of protein adsorption. These results should help to rationalize the design of biomaterials, biosensors, or protein separation devices.

  6. Adsorption of dispersing polyelectrolytes: stabilization of drilling fluids; Adsorption de polyelectrolytes dispersants: stabilisation des fluides de forage

    Energy Technology Data Exchange (ETDEWEB)

    Balastre, M.

    1999-11-10

    Instabilities of concentrated colloidal suspensions are a source of many industrial problems, as in drilling fluid formulations where aggregation and severe settling phenomena can occur. Low molecular weight polyelectrolyte dispersants are used to solve these problems, but their optimal use requires a better understanding of the phenomena that are involved. After materials characterization, adsorption mechanisms of two anionic polyelectrolytes (PANa, PSSNa) on a soluble substrate model, barium sulfate powder are studied. Barium sulfate is the principal additive used to adapt the density of drilling fluids. A simple model allows us to propose a distribution of the microscopic species at the interface. Presence of divalent ions induces the formation of a strong complex with the polyelectrolyte. Adsorption and electro-kinetic data are presented and exchange equilibrium are examined in relation with the surface uptake. The binding mechanism and the surface speciation of the polymer groups are deduced from the ion exchange analysis. The macroscopic behavior of suspensions on different conditions (volume fraction, ionic strength, dispersant concentration) is studied by settling and rheological measurements. The macroscopic properties are connected to structural aspects, and we show that dispersing effects are mostly related to electro-steric repulsion. The dispersion state depends on two principal factors adsorbed amounts and adsorbed layer properties, especially the excess charge, and the molecules conformation. (author)

  7. Covalently attached metalloporphyrins in LBL self-assembled redox polyelectrolyte thin films

    Energy Technology Data Exchange (ETDEWEB)

    Carballo, R.R.; Campodall' Orto, V.; Hurst, J.A.; Spiaggi, A.; Rezzano, I.N. [Departmento de Quimica Analitica y Fisicoquimica, Facultad de Farmacia y Bioquimica, Universidad de Buenos Aires, Junin 956, CP 1113 Buenos Aires (Argentina); Bonazzola, C. [INQUIMAE, Departamento de Quimica Inorganica, Analitica y Quimica Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellon 2, Ciudad Universitaria, CP 1428 Buenos Aires (Argentina)

    2008-06-30

    A formylporphyrin has been covalently bound to Poly (Allylamine Hydrochloride) (PAH) and electrostatically self-assembled polyelectrolyte films, containing the attached metalloporphyrin, have been constructed. The UV-vis absorption band at 390 nm has been followed as core porphyrin marker. The reflection-absorption IR spectra of the gold films modified with layer-by-layer (LBL) polyelectrolytes were recorded after 6 and 12 layers. Characteristic infrared absorbance bands of porphyrin, PAH and PVS became more evident on increasing the number of bilayers. The absorption bands at 750, 1214 and 2960 cm{sup -1}, attributed at {nu}(S-O), {nu}{sub s}(SO{sub 3}{sup -}) and {nu}(=NH{sub 2}{sup +}), respectively, showed a linear growth (R{sup 2} > 0.99) with the number of adsorbed layers. A lower correlation coefficient was observed for the band at 1585 cm{sup -1} attributed to Fe-protoporphyrin. In order to evaluate the electron transfer (ET) rate, the {delta}E{sub p} of the [Fe(CN){sub 6}]{sup 4-}/[Fe(CN){sub 6}]{sup 3-} couple in solution was measured after covering the electrode. A proportional increase of the {delta}E{sub p} with the number of layers is observed up to the 4th layer. After the second bilayer, the magnitude of the peak separation is highly related to the charge of the topmost layer. The method allowed controlling the film thickness via the number of deposited layers (LBL). The electrode described, resulted in a good catalyst for O{sub 2} reduction and sulfite oxidation. (author)

  8. Interfacial properties of bottle-brush polyelectrolytes

    DEFF Research Database (Denmark)

    Claesson, P. M.; Naderi, A.; Iruthayaraj, J.

    2007-01-01

    whereas on silica both electrostatic forces and interactions between silica and ethylene oxide chains drive the adsorption. On silica the adsorbed amount is very sensitive to solution ionic strength and pH. We also report on surface interactions and frictional forces obtained between surfaces coated...

  9. Adsorption of polyelectrolytes at liquid-liquid interfaces and its effect on

    NARCIS (Netherlands)

    Boehm, J.T.C.

    1974-01-01

    In this study we have investigated the adsorption behaviour of a number of synthetic polyelectrolytes at the paraffin oil-water interface and the properties of paraffin oil-in-water emulsions stabilized by these polyelectrolytes.Polyacrylic acid (PAA), polymethacrylic acid (PMA) and the copolymers o

  10. Adsorption of polyelectrolytes at liquid-liquid interfaces and its effect on emulsification

    NARCIS (Netherlands)

    Böhm, J.T.C.

    1974-01-01

    In this study we have investigated the adsorption behaviour of a number of synthetic polyelectrolytes at the paraffin oil-water interface and the properties of paraffin oil-in-water emulsions stabilized by these polyelectrolytes.

    Polyacrylic acid (PAA), polymethacrylic acid (PMA)

  11. Cylindrical cell model for the electrostatic free energy of polyelectrolyte complexes

    NARCIS (Netherlands)

    Biesheuvel, P.M.; Cohen Stuart, M.A.

    2004-01-01

    Associative phase separation (complex coacervation) in a mixture of oppositely charged polyelectrolytes can lead to different types of (inter-)polyelectrolyte complexes (soluble micelles, macroscopic precipitation). In a previous report [Langmuir 2004, 20, 2785-2791], we presented a model for the

  12. Zitongdong Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ The Zitongdong Block (Eastern Zitong Block) is located in the northwest of the Sichuan Basin. Tectonically, it is situated in the east part of Zitong Depression, southeast of mid-Longmenshan folded and faulted belt( as shown on Fig. 8 ), covering an area of 1 730 km2. The traffic is very convenient, the No. 108 national highway passes through the north of the block. Topographically, the area belongs to low hilly land at the elevation of 500-700 m.

  13. The effect of PEO block lengths on the size and stability of complex coacervate core micelles.

    Science.gov (United States)

    Adams, Dave J; Rogers, Sue H; Schuetz, Peter

    2008-06-15

    We report on a series of polyion complexes from mixtures of poly(ethylene oxide)-block-poly(N,N-diethylaminoethylmethacrylate) (PEO-PDEAMA) and poly(ethylene oxide)-block-poly(aspartic acid) (PEO-PAsp). As expected, the micelle size, polydispersity and stability are dependant on the relative and absolute lengths of the polyelectrolyte chains. However, we also demonstrate that whilst the length of the charged polyelectrolyte blocks is important, the length of the PEO chains is an equally relevant variable in determining both the size and stability of the final micelles as well as the degree of charge neutralisation at which micellisation occurs. We also show that the kinetics of formation can result in very different stability of the final micelles.

  14. On the difference in ionization properties between planar interfaces and linear polyelectrolytes

    Science.gov (United States)

    Borkovec, Michal; Daicic, John; Koper, Ger J. M.

    1997-01-01

    Ionizable planar interfaces and linear polyelectrolytes show markedly different proton-binding behavior. Planar interfaces protonate in a single broad step, whereas polyelectrolytes mostly undergo a two-step protonation. Such contrasting behavior is explained using a discrete-charge Ising model. This model is based on an approximation of the ionizable groups by point charges that are treated within a linearized Poisson–Boltzmann approximation. The underlying reason as to why planar interfaces exhibit mean-field-like behavior, whereas linear polyelectrolytes usually do not, is related to the range of the site–site interaction potential. For a planar interface, this interaction potential is much more long ranged if compared with that of the cylindrical geometry as appropriate to a linear polyelectrolyte. The model results are in semi-quantitative agreement with experimental data for fatty-acid monolayers, water-oxide interfaces, and various linear polyelectrolytes. PMID:9108004

  15. Morphology of cobalt ferrite nanoparticle-polyelectrolyte multilayered nanocomposites

    Science.gov (United States)

    Alcantara, G. B.; Paterno, L. G.; Fonseca, F. J.; Morais, P. C.; Soler, M. A. G.

    2011-05-01

    Novel magnetic nanocomposite films with controlled morphology were produced via the electrostatic layer-by-layer assembly of cationic CoFe 2O 4 nanoparticles and anionic poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonic acid) (PEDOT:PSS) complex. The electrostatic interaction between nanoparticle and the polyelectrolyte complex ensured a stepwise growth of the nanocomposite film with virtually identical amounts of materials being adsorbed at each deposition cycle as observed by UV-vis spectroscopy. AFM images acquired under the tapping mode revealed a globular morphology with dense and continuous layers of nanoparticles with voids being filled with polymeric material.

  16. New nanocomposites based on layered aluminosilicate and guanidine containing polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Khashirov, Azamat A.; Zhansitov, Azamat A.; Khashirova, Svetlana Yu. [Kabardino-Balkarian State University a. Kh.M. Berbekov, 173 Chernyshevskogo st., 360004, Nalchik (Russian Federation); Zaikov, Genadiy E. [N. M. Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, 4, Kosygin St., 119991, Moscow (Russian Federation)

    2014-05-15

    The new functional nanomaterials based on layered aluminosilicate and guanidine containing polyelectrolytes combining high bactericidal activity with an increased ability to bind to heavy metals and organic pollutants were received. To prove the chemical structure of the model compounds (zwitterionic delocalized resonance structures AG/MAG and PAG/PMAG), as well as the presence of such structures in nanocomposites received on their basis and the MMT, IR, {sup 1}H NMR spectroscopy, X-ray diffraction studies and nanoindentation/sclerometry followed by scanning the surface in the area of the indentation were used.

  17. Tailor-made polyelectrolyte microcapsules: from multilayers to smart containers.

    Science.gov (United States)

    Peyratout, Claire S; Dähne, Lars

    2004-07-19

    This review addresses the fabrication and properties of novel polyelectrolyte microcapsules, with an emphasis on their mechanical and permeability properties. Ease of preparation through layer-by-layer self assembly, accurate control over wall thickness as well as flexibility in the choice of constituents make these capsules very promising for numerous applications in materials and life science. Moreover, by engineering the inner and outer interfaces, these capsules can be used as microreactors for precipitation, crystallization, and polymerization reactions, as well as enzymatic, and heterogeneous catalysis.

  18. Preparation and Properties of Water-soluble Conjugated Polyelectrolyte

    Institute of Scientific and Technical Information of China (English)

    BAO Xiangjun; HONG Ruibin; HU Jianhua; ZHONG Yiping; LIU Ping; DENG Wenji

    2014-01-01

    The water-soluble conjugated polyelectrolyte, poly[3-(1′-ethyloxy-2′-N- methylimidazole) thiophene] (PEOIMT), was prepared. Its photophysical and electrochemical properties, and response characteristics to the external condition (e g, temperature response, solvent response and pH response), were investigated. The results show the PEOIMT belongs to the organic semiconductor. The interaction between the PEOIMT and the bovine serum albumin (BSA) was investigated using UV-vis spectroscopy. It was found that the PEOIMT could interact with the BSA. The PEOIMT can be used as a biosensor to detect the BSA.

  19. Encapsulation of Bacterial Spores in Nanoorganized Polyelectrolyte Shells (Postprint)

    Science.gov (United States)

    2009-05-27

    Baca, H.; Ashley, C.; Carnes , E.; Lopez, D.; Flemming, J.; Dunphy, D.; Singh, S.; Lopez, G.; Brozik, S.; Werner-Washburne, M.; Brinker, J. Science...concentration of aqueous polyelectrolytes was 2 mg/mL ( pH 6.8). All polymer samples were treated briefly in a sonicating bath and then vortex mixed before...positively charged and PGA is negatively charged at pH 6.5-7 due to amine and acid ionized Scheme 1 Figure 1. ζ-potential of a B. subtilis spore in DI water at

  20. Green preparation of antibiotic nanoparticle complex as potential anti-biofilm therapeutics via self-assembly amphiphile-polyelectrolyte complexation with dextran sulfate.

    Science.gov (United States)

    Cheow, Wean Sin; Hadinoto, Kunn

    2012-04-01

    Nanoscale antibiotic delivery has emerged as a promising therapeutic means to treat lung biofilm infection owed to its sputum penetrating ability. Due to the high antibiotic dosage requirement in anti-biofilm therapy, the most suitable formulation for this purpose is the antibiotic nanoparticles themselves, instead of the more extensively studied antibiotic-loaded nano-carriers, which often exhibit low drug loading. The present work details the preparation and characterization of antibiotic nanoparticle complex (or nanoplex) by self-assembly amphiphile-polyelectrolyte complexation process. Ofloxacin (OFX) and levofloxacin (LEV) are used as the antibiotics with dextran sulfate (DXT) as the polyelectrolyte. The nanoplex possesses high drug loading (up to 80%) and sizeenergy-minimal, solvent-free, and highly efficient as manifested in nearly 100% of drug is transformed into nanoplex. The effects of drug-to-polyelectrolyte charge ratio, pH, drug, and salt concentrations on the nanoplex characteristics (i.e. size, stability, drug loading) are investigated from which the optimal preparation conditions have been identified. Higher complexation efficiency and stronger agglomeration tendency are observed for LEV nanoplex owed to its higher hydrophobicity. The antibiotics are completely released from the nanoplex in aqueous salt solution within 3h and their antimicrobial activity is preserved upon complexation. The nanoplex is readily transformed into amorphous dry powders that remain stable after one-month storage owed to the high glass transition temperature. The antibiotic nanoplexes are highly charged enabling their subsequent functionalization for targeted delivery and controlled drug release purposes.

  1. Model Polyelectrolytes in Turbulent Couette Flow

    Science.gov (United States)

    Price, Brian; Hoagland, David A.

    1997-03-01

    Isolated polymer chains in strong flow are deformed significantly from their equilibrium conformations, imparting a pronounced change in the local velocity field. Turbulent drag reduction by dilute polymer solutions is an important example. The onset of drag reduction appears dependent on a characteristic shear stress at the wall τw for a given polymer. (Virk, P.S. AIChE Journal 21 1975) Length and time scales formed from τw and solvent kinematic viscosity provide different scalings of the onset with chain length. It is likely that length polydispersity could be responsible for the disparity among the previously reported results concerning the correct onset condition. We have employed preparative gel electrophoresis to produce samples of very low polydispersity to determine the onset scaling of drag reduction in turbulent couette flow. The same technique provides information about chain scission in turburlence, yielding an indirect indication of chain conformation.

  2. Zitongxi Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ Zitongxi Block (Western Zitong Block), is located in Zitong County, northwest of Sichuan Province (as shown on Fig. 8 ). Geologically. it is situated in the Zitong Depression, southwest of the middle Longmenshan faulted and folded belt, covering an area of 1 830 km2. Transportation is very convenient. A crisscross network of highways run through the block and the Baocheng railway is nearby. The climate is moderate. Most area belongs to hilly land with the elevation of 500-600 m.The Tongjiang River runs across the area.

  3. Specifics of solvation of sulfonated polyelectrolytes in water, dimethylmethylphosphonate, and their mixture: A molecular simulation study

    Science.gov (United States)

    Vishnyakov, Aleksey; Neimark, Alexander V.

    2008-04-01

    Sulfonated polyelectrolyte membranes (PEMs), such as Nafion and styrene-olefin block copolymers, are explored as permselective membranes for fuel cells as well as suitable barrier materials against chemical agents. The permselective properties of PEM are determined by their microphase segregation into hydrophilic and hydrophobic domains. We performed classical molecular dynamics simulations of solvation of the hydrophilic fragments of PEM exemplified on sulfonated polystyrene (sPS) with potassium, calcium, and aluminum as counterions, in water, phosphor-organic nerve agent simulant dimethylmethylphosphonate (DMMP), and their binary mixture. The force field for the sulfonate group has been developed by optimizing the potential parameters to fit the benzenesulfonate conformations obtained from the density functional theory. For a comparison, we considered perfluorosulfonate oligomers representing fragments of Nafion polymer. We found a noticeable difference between the geometries of the polymer backbone in different solvents. The polymer backbone is stiffer in DMMP for both sPS and Nafion. An anisotropic structuring of the solvent around the phenylsulfonate group is substantially stronger than around the Nafion sidechain due to the rigidity and the anisotropy of the phenylsulfonate group. The counterion significantly affects the conformations of solvated sPS: the rigidity of the backbone increases when potassium or calcium ions are replaced by trivalent aluminum ions.

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

    Science.gov (United States)

    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.

  5. The preparation of polyelectrolyte complexes carboxymethyl chitosan(CMC)-pectin by reflux method as a Pb (II) metal ion adsorbent

    Science.gov (United States)

    Hastuti, Budi; Mudasir, Siswanta, Dwi; Triyono

    2016-02-01

    Aim of this research is to synthesized a chemically stable polyelectrolyte complexs carboxymetyl chitosan CMC-pectin as Pb(II) ion adsorbent by reflux method. During synthesis process, the optimum mass ratio of CMC and pectin was pre-determined and the active groups of the CMC-pectin complex was characterized by using IR spectrofotometer. Finally, adsorption capacity of the adsorbent material for Pb (II) ions was studied under optimum condition, i.e. adsorbent mass, contact time, and pH. Result shows that CMC could be succesfully combined with pectin to produce CMC-pectin complex. The optimum mass ratio CMC: pectin to form the polyelectrolyte complexs CMC-pectin was 70% : 30%. The active groups identified in the CMC-pectin complex was a hydroxyl (OH) and carboxylate (-COOH) groups. The optimum conditions for Pb (II) ion absoprtion was 10 mg of the adsorbent mass, 75 min of contact time, and pH 5. This material can be effectively used as adsorbents for Pb (II) ions, where up to 91% Pb (II) metal ions was adsorbed from aqueous solution and the adsorption capacity of the adsorbent was 41.63 mg/g.

  6. Chengzikou Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ Chengzikou Block is located in the north of Hekou district, Dongying City, Shandong Province, adjacent to Bohai Bay. It can be geographically divided into three units: onshore, transitional zone and offshore ultrashallow zone, totally covering an area of 470 km2. The southern onshore area is low and gentle in topography;the northern shallow sea is at water depths of 2-8 m below sea level, and the transitional zone occupies more than 60% of the whole block. The climate belongs to temperate zone with seasonal wind. Highways are welldeveloped here, and the traffic is very convenient. The Chengzikou Block is about 80 km away from Dongying City and 290 km from Jinan City in the south. The northern offshore area of the block is 160 km away from Longkou port in the east and only 38 km away in the west from Zhuangxi port.

  7. Self-Assembly of Metallic and Magnetic Nanoparticles into Polyelectrolyte Multilayers

    Science.gov (United States)

    Riffard, Lucie

    Gold nanoparticles were wrapped with polyelectrolytes and were deposited on a substrate coated with polyelectrolyte multilayer films. The adsorption of the colloids on the surface was followed by AFM and UV-VIS spectroscopy. The results suggested that the deposition of particles on a surface was performed successfully just by using a very simple and quick dipping method. Using the same technique, magnetic particles were coated with polyelectrolytes and deposited on polyelectrolyte multilayer films. Once again the adsorption of the particles on polymer films was achieved and more complex assemblies were then built. They consisted of a succession of polyelectrolyte films and magnetic nanoparticles. As the colloids exhibit magnetic properties, the possibility of controlling properties of thin polymer films with a strong magnet is investigated. Magnetic colloids were embedded into a polymer assembly which undergoes the effects of a magnet. Its thickness changes were analyzed by ellipsometry when the sample was immersed in water. It appeared that magnetic nanoparticles were able to squeeze a polyelectrolyte thin film in presence of a magnet, despite the polymer chains resistance. This phenomenon can be used as nano-switches in various applications in medical field for example. In the future, it could be interesting to study the effect of an oscillating magnetic field on composite polyelectrolyte multilayer-magnetic particles. If the thickness fluctuates with the magnetic field, new applications towards the nanodisplacement of a fluid on a surface can be possible: the oscillations at the surface moving the adjacent fluid.

  8. Influence of higher valent ions on flexible polyelectrolyte stiffness and counter-ion distribution.

    Science.gov (United States)

    Chremos, Alexandros; Douglas, Jack F

    2016-04-28

    We investigate the influence of counter-ion valency on the flexibility of highly charged flexible polymer chains using molecular dynamics simulations that include both salt and an explicit solvent. As observed experimentally, we find that divalent counter-ions greatly reduce the chain persistence length, lp, in comparison with monovalent counter-ions. On the other hand, polyelectrolyte chains having trivalent counter-ions adopt a much more compact conformation than polyelectrolytes having monovalent and divalent counter-ions. We demonstrate that the tendency of polyelectrolyte chains to become deformed by proximal high valence counter-ions is due to chain "coiling" around the counter-ions. In particular, we find that the number of contacts that the proximal counter-ions have with the polyelectrolyte dictates the extent of chain coiling. This ion-binding induced coiling mechanism influences not only the conformational properties of the polyelectrolyte, but also the counter-ion distribution around the chain. Specifically, we find that higher valent counter-ions lead both to a counter-ion enrichment in close proximity to the polyelectrolyte and to a significant reduction in the spatial extent of the diffuse counter-ion cloud around the polyelectrolyte.

  9. Evaluation of an integrated extraction process for in-situ phenol removal with micellar solutions of PEO-PPO-PEO block copolymers

    NARCIS (Netherlands)

    Heerema, L.D.; Cakali, D.; Roelands, C.P.M.; Goetheer, E.L.V.; Verdoes, D.; Keurentjes, J.

    2010-01-01

    This paper evaluates the applicability of aqueous solutions of Pluronics for the removal of phenol in a separation and regeneration process. Experimental results show that Pluronic P103 micelles allow extraction of phenol from aqueous solutions at 30°C. The phenol can be released due to the transiti

  10. Longmenshan Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ Longmenshan Block is located in Jiange County of Jiangyou City in the northwest of Sichuan Basin. covering an area of 2 628 km2. Geologically, it is situated in the Mid-Longmenshan fault and fold belt, neighbouring Zitong Depression in its southeast. There are mountains surrounding its northwest , the rest area being hilly land,with the elevation of 500-700 m. The BaoCheng railway and the No. 108 highway run through the block, the traffic is very convenient.

  11. Impact of polyelectrolytes and their corresponding multilayers to human primary endothelial cells.

    Science.gov (United States)

    Nolte, Andrea; Hossfeld, Susanne; Schroeppel, Birgit; Mueller, Anne; Stoll, Dieter; Walker, Tobias; Wendel, Hans Peter; Krastev, Rumen

    2013-07-01

    The layer-by-layer technique, which allows simple preparation of polyelectrolyte multilayers, came into the focus of research for development of functionalized medical devices. Numerous literature exist that concentrate on the film build-up and the behaviour of cells on polyelectrolyte multilayers. However, in case of very soft polyelectrolyte multilayers, studies of the cell behaviour on these films are sometimes misleading with regard to clinical applications because cells do not die due to cytotoxicity but due to apoptosis by missing cell adhesion. It turns out that the adhesion in vitro, and thus, the viability of cells on polyelectrolyte multilayers is mostly influenced by their mechanical properties. In order to decide, which polyelectrolyte multilayers are suitable for implants, we take this problem into account by putting the substrates with soft films on top of pre-cultured human primary endothelial cells ('reverse assay'). Hence, the present work aims giving a more complete and reliable study of typical polyelectrolyte multilayers with regard to clinical applications. In particular, coatings consisting of hyaluronic acid and chitosan as natural polymers and sulfonated polystyrene and polyallylamine hydrochlorite as synthetic polymers were studied. The adsorption of polyelectrolytes was characterized by physico-chemical methods which show regular buildup. Biological examination of the native or modified polyelectrolyte multilayers was based on their effect to cell adhesion and morphology of endothelial cells by viability assays, immunostaining and scanning electron microscopy. Using the standard method, which is typically applied in literature--seeding cells on top of films--shows that the best adhesion and thus, viability can be achieved using sulfonated polystyrene/polyallylamine hydrochlorite. However, putting the films on top of endothelial cells reveals that hyaluronic acid/chitosan may also be suitable for clinical applications: This result is

  12. Catalytic polyelectrolyte multilayers at the bipolar membrane interface.

    Science.gov (United States)

    Abdu, Said; Sricharoen, Kittikun; Wong, John E; Muljadi, Eko S; Melin, Thomas; Wessling, Matthias

    2013-11-13

    Bipolar membranes are laminated anion and cation exchange membranes that split water at their interface very efficiently upon application of an electric field. This paper investigates the layer-by-layer (LbL) deposition of polyelectrolyte multilayers, as a tool to introduce molecularly thin catalyst groups at this interface of bipolar membranes. The bipolar membranes were prepared by first modifying an anion exchange membrane by consecutive dipping LbL assembly, then casting a thin highly charged intermediate layer followed by casting a cation exchange layer. The results reveal that polyelectrolytes of higher charge density coated on the anion exchange layer yield better performance. Several parameters of the LbL interface deposition were varied. Out of the investigated LbL assembly parameters, ionic strength and number of layers have shown the largest influence on catalytic activity as well as ionic selectivity. The membrane with two bilayers of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) and poly(ethyleneimine) (PEI), where the PEI was prepared in 0.5 M NaCl, gave rise to the best performance. Surprisingly, detailed data analysis at low electrical potential suggests that the interface layers of a bipolar membrane play a major role in its permselectivity. Previously, only the bulk thickness of the anion and cation exchange membrane was assumed to influence the bipolar membrane selectivity.

  13. Effect of Protein Supercharging on Interaction with Polyelectrolytes

    Science.gov (United States)

    Olsen, Bradley; Obermeyer, Allie; Mills, Carolyn; Dong, Xuehui

    Complexation of proteins with polyelectrolytes can lead to a liquid-liquid phase separation to generate a viscous complex coacervate phase rich in protein and polyelectrolyte. However, many proteins do not readily 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 chemically modified to generate a panel of proteins with varying surface charge, with both the average charge and charge distribution quantified by mass spectrometry. Proteins phase separated with the qP4VP and qPDMAEMA polycations when the ratio of negatively charged residues to positively charged residues was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger charge ratio (1.5-2.0). The model proteins were also encapsulated in complex coacervate core micelles. Dynamic light scattering was used to assess the formation of micelles with POEGMA- b-qP4VP and revealed micellar hydrodynamic radii of approximately 25-30 nm. Small angle neutron scattering and transmission electron microscopy were used to confirm the formation of spherical micelles.

  14. Study of sporadical properties of crosslinked polyelectrolyte multilayers

    Science.gov (United States)

    Balu, Deebika

    Polyelectrolyte multilayers (PEM) have become a highly studied class of materials due to the range of their applicability in many areas of research, including biology, chemistry and materials science. Recent advances in surface coatings have enabled modification of PEM surfaces to provide desirable properties such as controlled release, super-hydrophobicity, biocompatibility, antifouling and antibacterial properties. In the past decade, antimicrobial PEM coatings have been investigated as a safer alternative to the traditional disinfection methods that usually involve application of hazardous chemicals onto the surface to be cleaned. These antimicrobial coatings could be applied to common surfaces prone to colonization of bacteria (such as bench tops, faucet handles, etc) to supplement routine sanitization protocols by providing sustained antimicrobial activity. Vegetative bacteria (such as Escherichia coli) are more susceptible to antimicrobial agents than bacterial species that form spores. Hence, the antimicrobial activity of PEM coatings fabricated using Layer by Layer (LbL) technique were assayed using Bacillus anthracis spores (Sterne strain). In this thesis, the sporicidal effect of various polyelectrolyte multilayer coatings containing cross-linked polymers immersed in bleach have been evaluated as potential augmentation to existing disinfection methods.

  15. Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels

    Science.gov (United States)

    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.

  16. Effect of calcium/sodium ion exchange on the osmotic properties and structure of polyelectrolyte gels.

    Science.gov (United States)

    Horkay, Ferenc; Basser, Peter J; Hecht, Anne-Marie; Geissler, Erik

    2015-12-01

    We discuss the main findings of a long-term research program exploring the consequences of sodium/calcium ion exchange on the macroscopic osmotic and elastic properties, and the microscopic structure of representative synthetic polyelectrolyte (sodium polyacrylate, (polyacrylic acid)) and biopolymer gels (DNA). A common feature of these gels is that above a threshold calcium ion concentration, they exhibit a reversible volume phase transition. At the macroscopic level, the concentration dependence of the osmotic pressure shows that calcium ions influence primarily the third-order interaction term in the Flory-Huggins model of polymer solutions. Mechanical tests reveal that the elastic modulus is practically unaffected by the presence of calcium ions, indicating that ion bridging does not create permanent cross-links. At the microscopic level, small-angle neutron scattering shows that polyacrylic acid and DNA gels exhibit qualitatively similar structural features in spite of important differences (e.g. chain flexibility and chemical composition) between the two polymers. The main effect of calcium ions is that the neutron scattering intensity increases due to the decrease in the osmotic modulus. At the level of the counterion cloud around dissolved macroions, anomalous small-angle X-ray scattering measurements made on DNA indicate that divalent ions form a cylindrical sheath enveloping the chain, but they are not localized. Small-angle neutron scattering and small-angle X-ray scattering provide complementary information on the structure and interactions in polymer solutions and gels.

  17. Study the cooperative motion of long-chain polyelectrolyte in presence of small globular protein

    Science.gov (United States)

    Trabelsi, Saber; Bassalah, Mohamed Arbi; Aschi, Adel; Othman, Tahar; Gharbi, Abdelhafidh

    2016-12-01

    We study in this paper the effect of small globular protein on the dynamic properties of long-chain NaPSS in semidilute regime using Dynamic Light Scattering and viscometry in three phases respecting the pH of the medium. The scaling concept of the heterogeneous system is compared with the De Gennes argument for homogeneous polymer solutions. The results showed a positive and negative deviations to the De Gennes approach of the correlation length scale of mixture defined by (c/c*)δ. The macroscopic viscosity of protein and the potential electrostatic interaction are taken as principal factors affecting the cooperative motion of blobs. δ was discussed as the parameter responsible for the conformational change of polyelectrolyte chain subunit within blob. The theoretical analysis of the electrostatic interaction between protein and subunit gave one possible solution relating the deviation δ to the dimensionless coupling constant u as δ uu+1 and δ - 1/3 u/u+1 for a swollen and shrunk subunit, respectively. A good accordance of experimental values of δ to theoretical approach was found.

  18. Navier-Stokes solutions about the F/A-18 wing-LEX-fuselage configuration with multi-block structured grids

    Science.gov (United States)

    Ghaffari, Farhad; Luckring, James M.; Thomas, James L.; Bates, Brent L.; Biedron, Robert T.

    1991-01-01

    Three-dimensional thin-layer Navier-Stokes computations are presented for the F/A-18 configuration. The modeled configuration includes an accurate surface representation of the fuselage, leading-edge-extension, as well as the wing with and without leading-edge-flap deflection. A multi-block structured volume grid with various topologies is generated using transfinite interpolation technique. The flowfield domain is divided into twenty blocks, each representing a particular geometrical complexity of the configuration. The results are obtained from an algorithm for solving the compressible Navier-Stokes equations that incorporates an upwind-biased, flux-difference-splitting approach. In addition, a newly developed capability that allows for generalized surface patching among blocks is employed. Turbulent results are presented for flow conditions that correspond to recent NASA F/A-18 High Alpha Research Vehicle flight experiments. Good correlations between the computations and the flight test results are disclosed for both surface flow patterns as well as surface pressure distributions.

  19. Solvent controlled ion association in structured copolymers: Molecular dynamics simulations in dilute solutions

    Science.gov (United States)

    Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

    2015-09-01

    Tailoring the nature of individual segments within ion containing block co-polymers is one critical design tool to achieve desired properties. The local structure including the size and distribution of the ionic blocks, as well as the long range correlations, are crucial for their transport ability. Here, we present molecular dynamics simulations on the effects of varying the concentrations of the ionizable groups on the conformations of pentablock ionomer that consist of a center block of ionic sulfonated styrene tethered to polyethylene and terminated by a bulky substituted styrene in dilute solutions. Sulfonation fractions f (0 ≤ f ≤ 0.55), spanning the range from ionomer to polyelectrolytes, were studied. Results for the equilibrium conformation of the chains in water and a 1:1 mixture of cyclohexane and heptane are compared to that in implicit poor solvents with dielectric constants ɛ = 1.0 and 77.73. In water, the pentablock collapses with the sulfonated groups on the outer surface. As f increases, the ionic, center block increasingly segregates from the hydrophobic regions. In the 1:1 mixture of cyclohexane and heptane, the flexible blocks swell, while the center ionic block collapses for f > 0. For f = 0, all blocks swell. In both implicit poor solvents, the pentablock collapses into a nearly spherical shape for all f. The sodium counterions disperse widely throughout the simulation cell for both water and ɛ = 77.73, whereas for ɛ = 1.0 and mixture of cyclohexane and heptane, the counterions largely condense onto the collapsed pentablock.

  20. Adsorbed poly(aspartate) coating limits the adverse effects of dissolved groundwater solutes on Fe(0) nanoparticle reactivity with trichloroethylene.

    Science.gov (United States)

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

    2015-08-02

    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.

  1. Chadong Block

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    @@ The Chadong Block, located in the east of Qaidam Basin, Qinghai Province, covers an area of 12 452 km2. It is bounded by Kunlum Mountains in the south and the northwest is closely adjacent to Aimunike Mountain.Rivers are widely distributed, which always run in NWSE direction, including the Sulunguole, Qaidam and Haluwusu Rivers. The traffic condition is good, the Qinghai-Tibet highway stretching through the whole area and the Lan-Qing railway, 20-50 km away from the block, passing from north to west. A lot of Mongolia minority people have settled there, of which herdsmen always live nearby the Qaidam River drainage area.

  2. Interactions of phosphororganic agents with water and components of polyelectrolyte membranes.

    Science.gov (United States)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Gor, Gennady Yu; Neimark, Alexander V

    2011-11-24

    Interactions of nerve G-agents (sarin and soman) and their simulants DMMP (dimethyl methylphosphonate) and DIFP (diisopropyl fluorophosphate) with water and components of polyelectrolyte membranes are studied using ab initio calculations in conjunction with thermodynamic modeling using the conductor-like screening model for real solvents (COSMO-RS). To test reliability of COSMO-RS calculations, we measured the vapor-liquid equilibrium in DMMP-water mixtures and found quantitative agreement between computed and experimental results. Using COSMO-RS, we studied the interactions of phosphororganic agents with the characteristic fragments of perfluorinated and sulfonated polystyrene (sPS) polyelectrolytes, which are explored for protective clothing membranes. We found that both simulants, DIFP and DMMP, mimic the thermodynamic properties of G-agents reasonably well; however, there are certain specific differences that are discussed. We also suggested that sPS-based polyelectrolytes have less affinity for phosphorganic agents compared to prefluorinated polyelectrolytes similar to Nafion.

  3. Electrodeposition of a palladium nanocatalyst by ion confinement in polyelectrolyte multilayers.

    Science.gov (United States)

    Vago, Miguel; Tagliazucchi, Mario; Williams, Federico J; Calvo, Ernesto J

    2008-11-30

    A highly efficient and selective material for electrocatalytic hydrogenation has been prepared by depositing monodisperse palladium nanoparticles of size (6+/-1) nm by electrochemical reduction of PdCl(4)(2-) confined in a polyelectrolyte multilayer film.

  4. STUDY OF THE DIGESTED SLUDGE DEWATERING EFFECTIVENESS USING POLYELECTROLYTE GEL BASED ON ORGANIC POLYMERS

    Directory of Open Access Journals (Sweden)

    Marcin Głodniok

    2016-02-01

    Full Text Available The paper addresses the problems connected with sewage sludge dewatering. The premise of the study was the analysis of whether there are opportunities to increase the efficiency of dewatering sludge, a relatively low-cost involving the use of innovative polymers. The authors analyzed the impact of the new type of polyelectrolyte gel on the effectiveness of dewatering sludge. Laboratory studies were carried out at polyelectrolyte dose selection and laboratory testing on the press chamber designed to simulate the actual operation of sludge dewatering system. Two different doses of polyelectrolyte were tested for dose I – 4 ml/m3 and dose II – 8 ml/m3. The conducted analysis on laboratory press showed an increase of sludge dewatering efficiency by about 2% for dose no. I and by about 13% for dose no. II, in comparison to the test without polyelectrolyte.

  5. Study of the interface solid/solutions containing PEO-PPO block copolymers and asphaltenes by FTIR/ATR; Estudo de solucoes de copolimeros em bloco de PEO-PPO contendo asfaltenos por FTIR/DTA

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Janaina I.S.; Neto, Jessica S.G.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], E-mails: janaina_333@hotmail.com, kinha_dac_dm@hotmail.com; celias@ima.ufrj.br

    2011-07-01

    The formation of water/oil emulsions can cause problems in various stages of production, processing and refining of petroleum. In this study, the technique of Fourier transform infrared spectroscopy (FTIR) using the method of attenuated total reflectance (ATR) was applied to study the solid-solutions of block copolymers based on poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) interface and its interaction in this interface with asphaltenic fractions of petroleum. The solid is the crystal of the ATR. Initially, we determined the critical micelle concentration values of the copolymers, which were consistent those obtained by a tensiometer. Bottle Test was also performed to correlate the efficiency of PEO-PPO copolymers in the breaking of water/oil emulsions with its adsorption at the interfaces solutions. (author)

  6. BINDING OF IONIC SURFACTANTS ON OPPOSITELY CHARGED POLYELECTROLYTES OBSERVED BY FLUORESCENCE METHODS

    Institute of Scientific and Technical Information of China (English)

    Zhen Tong; Chao-yang Wang; Bi-ye Ren; Xin-xing Liu; Fang Zeng

    2003-01-01

    Our recent studies concerning the binding of ionic surfactants on oppositely charged polyelectrolytes observed with fluorescence techniques are reviewed. The cationic surfactants cetyltrimethylammonium bromide (CTAB),dodecyltrimethylammonium chloride (DTAC), and nonionic surfactant octaethylene glycol monododecyl ether (C12E8) were allowed to bind on anionic poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) and its pyrene and/or naphthalene labeled copolymers. The relative excimer emission intensity IE/IM of a cationic probe 1-pyrenemethylamine hydrochloride were chosen to monitor the binding process and the conformation change of surfactant-bound polyelectrolytes. The 1:1aggregation of polyelectrolyte-CTAB with respect to the charge was found as long as the CTAB concentration was slightly higher than its critical aggregation concentration (CAC). The intermolecular NRET indicated that the CTAB-bound polyelectrolytes aggregated together through the hydrophobic interaction between the CTAB tails. However, neither 1:1polyelectrolyte-DTAC aggregation nor intermolecular aggregation of DTAC-bound polyelectrolyte was observed owing to its weaker hydrophobicity of 12 carbon atoms in the tail, which is shorter than that of CTAB. As known from the fluorescence results, nonionic surfactant C12E8 did not bind on the anionic polyelectrolytes, but the presence of PAMPS promoted the micelle formation for C12E8 at the CAC slightly below its critical micelle concentration (CMC). The solid complex of dansyl labeled AMPS copolymer-surfactant exhibited a decrease in local polarity with increasing charge density of the polyelectrolyte or with alkane tail length of the surfactant. SAXS suggested a lamella structure for the AMPS copolymersurfactant solid complexes with a long period of 3.87 nm for CTAB and 3.04 nm for DTAC, respectively.

  7. Thermo-Responsive Complexes of c-Myc Antisense Oligonucleotide with Block Copolymer of Poly(OEGMA) and Quaternized Poly(4-Vinylpyridine).

    Science.gov (United States)

    Topuzogullari, Murat; Elalmis, Yeliz Basaran; Isoglu, Sevil Dincer

    2017-04-01

    Solution behavior of thermo-responsive polymers and their complexes with biological macromolecules may be affected by environmental conditions, such as the concentration of macromolecular components, pH, ion concentration, etc. Therefore, a thermo-responsive polymer and its complexes should be characterized in detail to observe their responses against possible environments under physiological conditions before biological applications. To briefly indicate this important issue, thermo-responsive block copolymer of quaternized poly(4-vinylpyridine) and poly(oligoethyleneglycol methyl ether methacrylate) as a potential nonviral vector has been synthesized. Polyelectrolyte complexes of this copolymer with the antisense oligonucleotide of c-Myc oncogene are also thermo-responsive but, have lower LCST (lower critical solution temperature) values compared to individual copolymer. LCST values of complexes decrease with molar ratio of macromolecular components and presence of salt. Dilution of solutions also affects solution behavior of complexes and causes a significant decrease in size and an increase in LCST, which indicates possible effects of severe dilutions in the blood stream.

  8. Morphology of cobalt ferrite nanoparticle-polyelectrolyte multilayered nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Alcantara, G.B.; Paterno, L.G. [Universidade de Brasilia, Instituto de Fisica, Brasilia-DF 70910-900 (Brazil); Fonseca, F.J. [Universidade de Sao Paulo, EPUSP, Depto de Engenharia de Sistemas Eletronicos, Sao Paulo-SP 05508-900 (Brazil); Morais, P.C. [Universidade de Brasilia, Instituto de Fisica, Brasilia-DF 70910-900 (Brazil); Soler, M.A.G., E-mail: soler@unb.b [Universidade de Brasilia, Instituto de Fisica, Brasilia-DF 70910-900 (Brazil)

    2011-05-15

    Novel magnetic nanocomposite films with controlled morphology were produced via the electrostatic layer-by-layer assembly of cationic CoFe{sub 2}O{sub 4} nanoparticles and anionic poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonic acid) (PEDOT:PSS) complex. The electrostatic interaction between nanoparticle and the polyelectrolyte complex ensured a stepwise growth of the nanocomposite film with virtually identical amounts of materials being adsorbed at each deposition cycle as observed by UV-vis spectroscopy. AFM images acquired under the tapping mode revealed a globular morphology with dense and continuous layers of nanoparticles with voids being filled with polymeric material. - Research Highlights: Novel magnetic nanocomposite films with controlled morphology assembled by layer-by-layer. Electrostatic interaction of cationic CoFe{sub 2}O{sub 4} nanoparticles and anionic (PEDOT:PSS). Globular morphology of dense layers of nanoparticles with voids being filled with polymeric material.

  9. Rapid polyelectrolyte-based membrane immunoassay for the herbicide butachlor.

    Science.gov (United States)

    Dzantiev, B B; Byzova, N A; Zherdev, A V; Hennion, M C

    2005-01-01

    Oppositely charged water-soluble polyelectrolytes were used in the developed membrane immunoenzyme assay for the herbicide butachlor. High-affinity and rapid binding between polyanion polymethacrylate and polycation poly(N-ethyl-4-vinylpyridinium) was applied to separate reacted and free immunoreactants. Competitive immunoassay format with peroxidase-labeled antigen was realized. The insoluble colored product of the peroxidase reaction was formed by bound labeled immune complexes and was reflectometrically detected. The assay combines short duration (15 min), high sensitivity (0.03 g/mL) and availability for out-of-laboratory testing. Different image processing algorithms were used to determine the herbicide content. Low variation coefficients of the measurements in the proposed quantitative assay, namely 4.8-9.0% for the range of antigen concentrations from 0.1 to 3.0 ng/mL, are evidence of the assay effectiveness. Possibility to control the butachlor content in mineral, artesian, and drinking water was demonstrated.

  10. Polyelectrolyte membranes based on hydrocarbon polymer containing fullerene

    Science.gov (United States)

    Saga, Shota; Matsumoto, Hidetoshi; Saito, Keiichiro; Minagawa, Mie; Tanioka, Akihiko

    In the present study, composite polyelectrolyte membranes were prepared from sulfonated polystyrene and fullerene. The additive effect of the fullerene on the membrane properties - electric resistance, mechanical strength, oxidation resistance, and methanol permeability - were measured. The addition of fullerene improved the oxidation resistance, and reduced the methanol crossover. The mechanical strength of the fullerene-composite membrane, on the other hand, was not improved. The direct methanol fuel cell (DMFC) based on a 1.4 wt% fullerene-composite membrane showed the highest power density of 47 mW cm -2 at the current density of 200 mA cm -2 (this value is 60% of the Nafion-based DMFC). The transmission electron microscopy (TEM) observations suggest that the improved dispersity of the fullerene and the reduced number of micropores in the membranes would improve its performance in the fuel cell.

  11. Polyelectrolyte coating of ferumoxytol nanoparticles for labeling of dendritic cells

    Science.gov (United States)

    Celikkin, Nehar; Jakubcová, Lucie; Zenke, Martin; Hoss, Mareike; Wong, John Erik; Hieronymus, Thomas

    2015-04-01

    Engineered magnetic nanoparticles (MNPs) are emerging to be used as cell tracers, drug delivery vehicles, and contrast agents for magnetic resonance imaging (MRI) for enhanced theragnostic applications in biomedicine. In vitro labeling of target cell populations with MNPs and their implantation into animal models and patients shows promising outcomes in monitoring successful cell engraftment, differentiation and migration by using MRI. Dendritic cells (DCs) are professional antigen-presenting cells that initiate adaptive immune responses. Thus, DCs have been the focus of cellular immunotherapy and are increasingly applied in clinical trials. Here, we addressed the coating of different polyelectrolytes (PE) around ferumoxytol particles using the layer-by-layer technique. The impact of PE-coated ferumoxytol particles for labeling of DCs and Flt3+ DC progenitors was then investigated. The results from our studies revealed that PE-coated ferumoxytol particles can be readily employed for labeling of DC and DC progenitors and thus are potentially suitable as contrast agents for MRI tracking.

  12. Voltage-controlled metal binding on polyelectrolyte-functionalized nanopores.

    Science.gov (United States)

    Actis, Paolo; Vilozny, Boaz; Seger, R Adam; Li, Xiang; Jejelowo, Olufisayo; Rinaudo, Marguerite; Pourmand, Nader

    2011-05-17

    Most of the research in the field of nanopore-based platforms is focused on monitoring ion currents and forces as individual molecules translocate through the nanopore. Molecular gating, however, can occur when target analytes interact with receptors appended to the nanopore surface. Here we show that a solid state nanopore functionalized with polyelectrolytes can reversibly bind metal ions, resulting in a reversible, real-time signal that is concentration dependent. Functionalization of the sensor is based on electrostatic interactions, requires no covalent bond formation, and can be monitored in real time. Furthermore, we demonstrate how the applied voltage can be employed to tune the binding properties of the sensor. The sensor has wide-ranging applications and, its simplest incarnation can be used to study binding thermodynamics using purely electrical measurements with no need for labeling.

  13. Changes in the Activity and Structure of Urease in the Interaction with Polyelectrolytes

    Science.gov (United States)

    Saburova, E. A.; Tikhonenko, S. A.; Dybovskaya, Yu. N.; Sukhorukov, B. I.

    2008-03-01

    The influence of polyelectrolytes on the structural and catalytic characteristics of urease ( Canavalia ensiformis) was studied by the methods of steady-state kinetics, fluorescence spectroscopy, and circular dichroism. It was shown that, of the four polyelectrolytes studied, two of which were negatively charged (polystyrene sulfonate and dextran sulfate) and two were positively charged (polyallylamine (PAA) and polydiallyl dimethylammonium chloride), only PAA was a potent urease inhibitor: 0.5 μg/ml of PAA provided a 50% degree of inhibition for enzyme at neutral pH. It was found that polyelectrolyte did not inhibit urease in the presence of micromolar concentrations of ammonium chloride. Based on the experimental data and the calculated structure of urease from Canavalia ensiformis and on the identity with the amino acid sequence of urease from Bacillus pasteurii, the mechanism of urease inactivation by the PAA polyelectrolyte is discussed. This mechanism does not resemble the inhibiting action of polyelectrolytes on the previously studied oligomeric proteins—lactate dehydrogenase, glutamate dehydrogenase, and hemoglobin. It is proposed that the specific cation-binding sites determining the structural dynamics of the enzyme-polyelectrolyte complex play the regulating role in the urease molecule.

  14. A stable nanoplatform for antitumor activity using PEG-PLL-PLA triblock co-polyelectrolyte.

    Science.gov (United States)

    Lim, Chaemin; Sim, Taehoon; Hoang, Ngoc Ha; Oh, Kyung Taek

    2017-05-01

    Polyelectrolyte has been proposed as an efficient approach for various types of drug formulations. However, one drawback of using the conventional polyelectrolyte for drug delivery is its dissociation in in vivo conditions by counter ions due to the lack of self-assembling aggregation force. In this study, we reported a stable nanoplatform based on triblock co-polyelectrolyte composed of a poly(ethylene glycol), poly(l-lysine), and poly(lactic acid). These co-polyelectrolytes formed stable aggregates through the hydrophobic interaction of PLA and showed consistent particle sizes under a high salt concentration. In addition, the doxorubicin (Dox) loaded triblock co-polyelectrolyte demonstrated enhanced cellular uptake and drug cytotoxicity with a positive charge from the poly(l-lysine) layer. In vivo, the triblock aggregates exhibited intensive accumulation at the targeted tumor site for 24h with good antitumor therapeutic efficacy. Therefore, the prepared stable triblock co-polyelectrolyte may have considerable potential as a nanomedicinal platform for anticancer and multi-drug combination therapy. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Encapsulation of curcumin in polyelectrolyte nanocapsules and their neuroprotective activity

    Science.gov (United States)

    Szczepanowicz, Krzysztof; Jantas, Danuta; Piotrowski, Marek; Staroń, Jakub; Leśkiewicz, Monika; Regulska, Magdalena; Lasoń, Władysław; Warszyński, Piotr

    2016-09-01

    Poor water solubility and low bioavailability of lipophilic drugs can be potentially improved with the use of delivery systems. In this study, encapsulation of nanoemulsion droplets was utilized to prepare curcumin nanocarriers. Nanosize droplets containing the drug were encapsulated in polyelectrolyte shells formed by the layer-by-layer (LbL) adsorption of biocompatible polyelectrolytes: poly-L-lysine (PLL) and poly-L-glutamic acid (PGA). The size of synthesized nanocapsules was around 100 nm. Their biocompatibility and neuroprotective effects were evaluated on the SH-SY5Y human neuroblastoma cell line using cell viability/toxicity assays (MTT reduction, LDH release). Statistically significant toxic effect was clearly observed for PLL coated nanocapsules (reduction in cell viability about 20%-60%), while nanocapsules with PLL/PGA coating did not evoke any detrimental effects on SH-SY5Y cells. Curcumin encapsulated in PLL/PGA showed similar neuroprotective activity against hydrogen peroxide (H2O2)-induced cell damage, as did 5 μM curcumin pre-dissolved in DMSO (about 16% of protection). Determination of concentration of curcumin in cell lysate confirmed that curcumin in nanocapsules has cell protective effect in lower concentrations (at least 20 times) than when given alone. Intracellular mechanisms of encapsulated curcumin-mediated protection engaged the prevention of the H2O2-induced decrease in mitochondrial membrane potential (MMP) but did not attenuate Reactive Oxygen Species (ROS) formation. The obtained results indicate the utility of PLL/PGA shell nanocapsules as a promising, alternative way of curcumin delivery for neuroprotective purposes with improved efficiency and reduced toxicity.

  16. Ionic Current Rectification in a pH-Tunable Polyelectrolyte Brushes Functionalized Conical Nanopore: Effect of Salt Gradient.

    Science.gov (United States)

    Lin, Jeng-Yang; Lin, Chih-Yuan; Hsu, Jyh-Ping; Tseng, Shiojenn

    2016-01-19

    The behavior of ionic current rectification (ICR) in a conical nanopore with its surface modified by pH-tunable polyelectrolyte (PE) brushes connecting two large reservoirs subject to an applied electric field and a salt gradient is investigated. Parameters including the solution pH, types of ionic species, strength of applied salt gradient, and applied potential bias are examined for their influences on the ionic current and rectification factor, and the mechanisms involved are investigated comprehensively. The ICR behavior depends highly on the charged conditions of the PE layer, the level of pH, the geometry of nanopore, and the thickness of the double layer. In particular, the distribution of ionic species and the local electric field near the nanopore openings play a key role, yielding profound and interesting results that are informative to device design as well as experimental data interpretation.

  17. Fabrication and Characterization of Electrospun Semiconductor Nanoparticle—Polyelectrolyte Ultra-Fine Fiber Composites for Sensing Applications

    Directory of Open Access Journals (Sweden)

    Caroline L. Schauer

    2011-10-01

    Full Text Available Fluorescent composite fibrous assembles of nanoparticle-polyelectrolyte fibers are useful multifunctional materials, utilized in filtration, sensing and tissue engineering applications, with the added benefits of improved mechanical, electrical or structural characteristics over the individual components. Composite fibrous mats were prepared by electrospinning aqueous solutions of 6 wt% poly(acrylic acid (PAA loaded with 0.15 and 0.20% v/v, carboxyl functionalized CdSe/ZnS nanoparticles (SNPs. The resulting fluorescent composite fibrous mats exhibits recoverable quenching when exposed to high humidity. The sensor response is sensitive to water concentration and is attributed to the change in the local charges around the SNPs due to deprotonation of the carboxylic acids on the SNPs and the surrounding polymer matrix.

  18. Fabrication of surfaces with extremely high contact angle hysteresis from polyelectrolyte multilayer.

    Science.gov (United States)

    Wang, Liming; Wei, Jingjing; Su, Zhaohui

    2011-12-20

    High contact angle hysteresis on polyelectrolyte multilayers (PEMs) ion-paired with hydrophobic perfluorooctanoate anions is reported. Both the bilayer number of PEMs and the ionic strength of deposition solutions have significant influence on contact angle hysteresis: higher ionic strength and greater bilayer number cause increased contact angle hysteresis values. The hysteresis values of ~100° were observed on smooth PEMs and pinning of the receding contact line on hydrophilic defects is implicated as the cause of hysteresis. Surface roughness can be used to further tune the contact angle hysteresis on the PEMs. A surface with extremely high contact angle hysteresis of 156° was fabricated when a PEM was deposited on a rough substrate coated with submicrometer scale silica spheres. It was demonstrated that this extremely high value of contact angle hysteresis resulted from the penetration of water into the rough asperities on the substrate. The same substrate hydrophobized by chemical vapor deposition of 1H,1H,2H,2H-perfluorooctyltriethoxysilane exhibits high advancing contact angle and low hysteresis.

  19. Cationic Amphiphiles Increase Activity of Aminoglycoside Antibiotic Tobramycin in the Presence of Airway Polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Purdy Drew, Kirstin R.; Sanders, Lori K.; Culumber, Zachary W.; Zribi, Olena; Wong, Gerard C.L.; (UIUC)

    2009-06-17

    It is empirically known that anionic polyelectrolytes present in cystic fibrosis (CF) airways due to bacterial infection significantly decrease the activity of cationic antimicrobials via electrostatic binding. In this work, we use synchrotron small-angle X-ray scattering to investigate the interaction between tobramycin, an aminoglycoside antibiotic commonly administered to CF patients via inhalation, with DNA, which is found in high concentrations in the CF airway. We find that interactions between DNA and tobramycin are significantly modified by the presence of mixtures of amphiphilic molecules. We measure a hierarchy of self-assembled structures formed between tobramycin, DNA, and the amphiphile mixtures and show how interactions between these components can be controlled. Results indicate that mixtures of cationic and negative curvature amphiphiles optimized for DNA binding via charge matching and curvature matching can competitively displace bound tobramycin from DNA and thereby drastically suppress tobramycin-DNA binding and resultant antimicrobial inactivation. Growth inhibition assays confirm the increased activity of tobramycin in the presence of DNA with the addition of the amphiphiles. These results suggest that optimized cationic amphiphile solutions have the potential to enhance antimicrobial function in highly infected environments that contain increased concentrations of anionic inflammatory polymers.

  20. Cationic Amphiphiles Increase Activity of Aminoglycoside Antibiotic Tobramycin in the Presence of Airway Polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Drew, K.R.Purdy; Sanders, L.K.; Culumber, Z.W.; Zribi, O.; Wong, G.C.L.

    2009-05-21

    It is empirically known that anionic polyelectrolytes present in cystic fibrosis (CF) airways due to bacterial infection significantly decrease the activity of cationic antimicrobials via electrostatic binding. In this work, we use synchrotron small-angle X-ray scattering to investigate the interaction between tobramycin, an aminoglycoside antibiotic commonly administered to CF patients via inhalation, with DNA, which is found in high concentrations in the CF airway. We find that interactions between DNA and tobramycin are significantly modified by the presence of mixtures of amphiphilic molecules. We measure a hierarchy of self-assembled structures formed between tobramycin, DNA, and the amphiphile mixtures and show how interactions between these components can be controlled. Results indicate that mixtures of cationic and negative curvature amphiphiles optimized for DNA binding via charge matching and curvature matching can competitively displace bound tobramycin from DNA and thereby drastically suppress tobramycin-DNA binding and resultant antimicrobial inactivation. Growth inhibition assays confirm the increased activity of tobramycin in the presence of DNA with the addition of the amphiphiles. These results suggest that optimized cationic amphiphile solutions have the potential to enhance antimicrobial function in highly infected environments that contain increased concentrations of anionic inflammatory polymers.

  1. Ultrathin free-standing polyelectrolyte nanocomposites: a novel method for preparation and characterization of assembly dynamics.

    Science.gov (United States)

    Ferri, James K; Dong, Wen-Fei; Miller, Reinhard

    2005-08-11

    We present a new opportunity for the investigation of the dynamics of electrostatic ultrathin-film assembly and the elucidation of time scales required for layer-by-layer adsorption of polyelectrolytes using a novel pendant drop technique which allows for the synthesis of free-standing nanocomposites. In short, a charged molecular template, i.e., a lipid monolayer, is deposited on a pendant drop and compressed to present a defined surface charge density to the subphase of the drop. The subphase is then cycled alternatively between solutions of polycations, saline, and polyanions by injection and withdrawal of liquid from coaxial capillaries on which the drop was formed, resulting in encapsulation of the drop volume by a polymeric composite membrane. The in situ dynamics of the process are followed by axisymmetric drop shape analysis. As a model, nanocomposites of dimyristoyl phosphatidyl glycerol-(polyallylamine hydrochloride/polystyrene sulfonate)(n=1-3) were prepared. The characteristic time scales for assembly range from 1 to 4 min and increase with film thickness. It is also demonstrated that small-amplitude (>1%) perturbations in the film density during adsorption prolong the assembly. Both these results underscore the nonequilibrium nature of these materials.

  2. A two-step process for controlling the surface smoothness of polyelectrolyte-based microcapsules.

    Science.gov (United States)

    Lacík, I; Anilkumar, A V; Wang, T G

    2001-01-01

    Biocompatibility is one of the crucial requirements to be fulfilled when designing devices for immunoisolation of transplanted cells. The quality of the capsule surface (smoothness/roughness) influences the nature of cell overgrowth on it by immunocytes, which eventually may lead to the transplant failure. A microcapsule has been developed based on the polyelectrolyte complexation of the polyanions sodium alginate and cellulose sulphate with the polycation poly(methylene-co-guanidine), which was successfully tested in rodent animal models. Recently, the principles for controlling the surface smoothness of these capsules has been identified. This paper reports on a two-step process used for production of stable capsules with improved surface properties. The methodology involves separating the process of drop shape recovery and precursor capsule formation from the process of membrane formation by applying a two-reactor design. The multi-loop reactors are connected in series, and the process separation is given by the different composition of cation solutions flowing in each reactor. This process enables one to prepare the microcapsule immunoisolation device, which can differ in the extent of surface roughness and, thus, is suitable for studying the effect of surface morphology of the immunoisolation device on cell overgrowth. The effect of this process on the capsule permeability has also been evaluated.

  3. Ionic Conductivity of Water-Soluble Fully Conjugated Heterocyclic Aromatic Polyelectrolytes

    Science.gov (United States)

    Bai, S. J.; Chen, Y. S.; Sun, J. P.; Dang, T. D.; Arnold, F. E.

    2002-03-01

    Fully conjugated poly[(1,7-dihydrobenzo[1,2-d:4,5-d']diimidazole-2,6-diyl)- 2-(2-sulfo)-p-phenylene], sPBI, has a para-catenated backbone. This rod-like polymer displays superior thermal and solvent stabilities. The stabilities hamper its processing for critical applications. Chemical derivative of the sPBI was achieved using pendants of propane-sulfonated Li^+ ionomer for a water-soluble polyelectrolyte, sPBI-PS(Li^+). sPBI-PS(Li^+) aqueous solutions were cast into freestanding films. Room-temperature direct current conductivity parallel to the film surface σ _|| was as high as 9.7 x 10-5 S/cm. Constant-voltage measurements indicated that σ _|| was mainly ionic. sPBI-PS(Li^+) doped with Li salts showed a σ _|| of 3 ~8 mS/cm. X-ray scattering revealed that the cast films were in-plane isotropic but out-of-the plane anisotropic with the rigid-rod backbone lying in the plane of the films. The anisotropic structure caused the conductivity transverse to the film surface was 10-3 ~ 10-4 to that of σ _||. Benzene-1,3,5-tricarboxylic acid with functional groups was added in the polycondensation reaction leading to heteroaromatic copolymer with fully conjugated but acticulated backbone. Cast films of the articulated copolymer had three-dimensionally isotropic σ as high as 3 mS/cm.

  4. Quantification of hydrolytic charge loss of DMAEA-Q-based polyelectrolytes by proton NMR spectroscopy and implications for colloid titration.

    Science.gov (United States)

    Saveyn, Hans; Hendrickx, Pieter M S; Dentel, Steven K; Martins, José C; Van der Meeren, Paul

    2008-05-01

    Copolymers of acrylamide and quaternised dimethylaminoethyl acrylate (DMAEA-Q) constitute an economically important range of cationic polyelectrolytes used in sludge conditioning. The latter treatment involves charge neutralisation and bridging induced by these polymers. Since both of these phenomena rely on charge-driven sorption onto the negatively charged colloidal particles, the accurate assessment of their charge density is of primary importance in polyelectrolyte characterisation. The experimental determination of this characteristic generally relies on colloidal charge titration, in which the cationic polymer is titrated against an anionic polymer. Hereby, one of the requirements to have a stoichiometric reaction between the oppositely charged polymers is a sufficiently low polymer concentration. In this study, it is shown that such a low polymer concentration may entail a pronounced hydrolysis effect for DMAEA-Q-based polymers, which leads to a release of the cationic side groups and hence causes considerable errors on the charge titration results. Proton nuclear magnetic resonance spectroscopy was applied to investigate the fast hydrolysis kinetics of DMAEA-Q polymers together with time-dependent charge titration measurements. Diffusion NMR spectroscopy was used to assist in establishing the nature of the hydrolysis compounds. The results from both techniques indicate that a high degree of hydrolysis is reached within minutes after dilution of a concentrated polymer stock solution into aqueous solutions of slightly acidic to neutral pH values. Therefore, a modification to the classic colloid titration procedure is proposed, using a buffered dilution liquid to avoid polymer hydrolysis. It is shown that a buffer pH value of 4.5 avoids not only polymer hydrolysis effects but also possible protonation of the anionic titrant, thereby avoiding overestimation of the charge density. By means of this procedure, reproducible and time-independent charge titration

  5. Polyelectrolytes: Influence on Evaporative Self-Assembly of Particles and Assembly of Multilayers with Polymers, Nanoparticles and Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Tatiana Bukreeva

    2010-12-01

    Full Text Available Assembling polyelectrolyte multilayers in a bottom-up approach is reported for polymers, particles, nanoparticles, and carbon nanotubes. Effects of polyelectrolyte multilayers on evaporative self-assembly of particles, which are of interest to a number of applications including photonic crystals, films and substrates, are investigated. Polyelectrolyte multilayer coatings bring multifunctionality to spherical particles and planar films. Studying the construction of polyelectrolyte assemblies is convenient in the planar layout: it is reported here for incorporation of gold and magnetic nanoparticles as well as of carbon nanotubes. Gold nanoparticles concentration is controlled within the films. Potential applications of both spherical structures and planar films are highlighted.

  6. Nanochemistry in confined environments: polyelectrolyte brush-assisted synthesis of gold nanoparticles inside ordered mesoporous thin films.

    Science.gov (United States)

    Calvo, Alejandra; Fuertes, M Cecilia; Yameen, Basit; Williams, Federico J; Azzaroni, Omar; Soler-Illia, Galo J A A

    2010-04-20

    A robust and straightforward strategy allowing the controlled confinement of metal nanoparticles within the 3D framework of mesoporous films is presented. The chemical methodology is based on the inner surface modification of mesoporous silica films with polyelectrolyte brushes. We demonstrate that the macromolecular building blocks significantly enhance the site-selective preconcentration of nanoparticle precursors in the inner environment of the mesoporous film. Then, chemical reduction of the preconcentrated precursors led to the formation of metal nanoparticles locally addressed in the mesoporous structure. We show that the synergy taking place between two versatile functional nanobuilding blocks (ordered mesocavities and polymer brushes) can produce stable embedded nanoparticles with tuned optical properties in a very simple manner. As a general framework, the strategy can be easily adapted to different sets of polymer brushes and mesoporous films in order to regulate the monomer-precursor interactions and, consequently, manipulate the site-selective character of the different chemistries taking place in the film. We consider that the "integrative chemistry" approach described in this work provides new pathways to manipulate the physicochemical characteristics of hybrid organic-inorganic advanced functional assemblies based on the rational design of chemistry and topology in confined environments.

  7. Triazine-based Polyelectrolyte as an Efficient Cathode Interfacial Material for Polymer Solar Cells.

    Science.gov (United States)

    Chakravarthi, Nallan; Aryal, Um Kanta; Gunasekar, Kumarasamy; Park, Ho-Yeol; Gal, Yeong-Soon; Cho, Young-Rae; Yoo, Seong Il; Song, Myungkwan; Jin, Sung-Ho

    2017-07-26

    A novel polyelectrolyte containing triazine (TAZ) and benzodithiophene (BDT) scaffolds with polar phosphine oxide (P═O) and quaternary ammonium ions as pendant groups, respectively, in the polymer backbone (PBTAZPOBr) was synthesized to use it as a cathode interfacial layer (CIL) for polymer solar cell (PSC) application. Owing to the high electron affinity of the TAZ unit and P═O group, PBTAZPOBr could behave as an effective electron transport material. Due to the polar quaternary ammonium and P═O groups, the interfacial dipole moment created by PBTAZPOBr substantially reduced the work function of the metal cathode to afford better energy alignment in the device, thus enabling electron extraction and reducing recombination of excitons at the photoactive layer/cathode interface. Consequently, the PSC devices based on the poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl]:[6,6]-phenyl-C71-butyric acid methyl ester (PTB7:PC71BM) system with PBTAZPOBr as CIL displayed simultaneously enhanced open-circuit voltage, short-circuit current density, and fill factor, whereas the power conversion efficiency increased from 5.42% to 8.04% compared to that of the pristine Al device. The outstanding performance of PBTAZPOBr is attributed not only to the polar pendant groups of BDT unit but also to the TAZ unit linked with the P═O group of PBTAZPOBr, demonstrating that functionalized TAZ building blocks are very promising cathode interfacial materials (CIMs). The design strategy proposed in this work will be helpful to develop more efficient CIMs for high performance PSCs in the future.

  8. CO2 switchable dual responsive polymers as draw solutes for forward osmosis desalination.

    Science.gov (United States)

    Cai, Yufeng; Shen, Wenming; Wang, Rong; Krantz, William B; Fane, Anthony G; Hu, Xiao

    2013-09-28

    Low molecular weight dual responsive polymers, after purging with CO2, become polyelectrolytes with high osmolality, which can be used as draw solutes for seawater desalination. These polymers precipitate above their Lower Critical Solution Temperature (LCST) after removal of CO2 via purging with inert gas for ease of recovery and reuse.

  9. Poly-electrolytes for fuel cells: tools and methods for characterization; Polyelectrolytes pour piles a combustible: outils et methodes de caracterisation

    Energy Technology Data Exchange (ETDEWEB)

    Marechal, M.

    2004-12-15

    The research works reported in the manuscript are a contribution to the study of poly-electrolytes for Proton Exchange Membrane Fuel Cells (PEMFC). They are supported by two investigation tools, i.e. the study of model molecules and accurate conductivity measurements. With regard to the material science domain, the optimization of poly-sulfone sulfonation procedure allows chain breaking to be reduced and even eliminated while obtaining reproducible sulfonation degrees. It is thus possible to improve the mechanical properties of the dense membrane elaborated with these poly-electrolytes before performing the tests on the MEA (Membrane Electrode Assembly). In parallel, the functionalization of microporous silicon made it possible to prepare poly-electrolytes reinforced by the mechanical strength of the silicon separator. With regard to the physicochemical and electrochemical characterizations, the model molecules, with the same functions and groups than for associated polymers, make it possible to amplify the electrochemical or thermal phenomena vs. the corresponding polymers. Thus, they simulate an accelerated ageing of the poly-electrolytes. The development of a new conductivity measurement set allows conductivity to be obtained with a great accuracy, in a wide range of temperature and relative humidity. (author)

  10. Hydrophilic drug encapsulation in shell-core microcarriers by two stage polyelectrolyte complexation method.

    Science.gov (United States)

    Dalmoro, Annalisa; Sitenkov, Alexander Y; Cascone, Sara; Lamberti, Gaetano; Barba, Anna Angela; Moustafine, Rouslan I

    2017-02-25

    In this study a protocol exploiting the combination of the ultrasonic atomization and the complexation between polyelectrolytes was developed to efficiently encapsulate a hydrophilic chemotherapeutic agent essentially used in the treatment of colon cancer, 5-fluorouracil, in enteric shell-core alginate-based microcarriers. The atomization assisted by ultrasound allowed to obtain small droplets by supplying low energy and avoiding drug degradation. In particular microcarriers were produced in a home-made apparatus where both the core (composed of alginate, drug, and Pluronic F127) and shell (composed of only alginate) feed were separately sent to the coaxial ultrasonic atomizer where they were nebulized and placed in contact with the complexation bulk. With the aim to obtain microstructured particles of alginate encapsulating 5-fluorouracil, different formulations of the first complexation bulk were tested; at last an emulsion made of a calcium chloride aqueous solution and dichloromethane allowed to reach an encapsulation efficiency of about 50%. This result can be considered very interesting considering that in literature similar techniques gave 5-fluorouracil encapsulation efficiencies of about 10%. Since a single complexation stage was not able to assure microcarriers gastroresistance, the formulation of a second complexation bulk was evaluated. The solution of cationic and pH-insoluble Eudragit® RS 100 in dichloromethane was chosen as bulk of second-stage complexation obtaining good enteric properties of shell-core microcarriers, i.e. a 5-FU cumulative release at pH 1 (simulating gastric pH) lower than 35%. The formation of interpolyelectrolyte complex (IPEC) between countercharged polymers and the chemical stability of 5-FU in microcarriers were confirmed by FTIR analysis, the presence of an amorphous dispersion of 5-FU in prepared microparticles was also confirmed by DSC. Finally, shell-core enteric coated microcarriers encapsulating 5-fluorouracil were used

  11. Topological structures of boundary value problems in block elements

    Science.gov (United States)

    Babeshko, V. A.; Evdokimova, O. V.; Babeshko, O. M.

    2016-10-01

    Block structures are considered; a boundary value problem for a system of inhomogeneous partial differential equations with constant coefficients is formulated in each block of a structure. The problem of matching solutions to boundary value problems in blocks with each other by topological study of the properties of solutions in the block structure is examined in the conditions of correct solvability of boundary value problems in blocks of the block structure. Some new properties of solutions to boundary value problems in block structures are found that are important for applications.

  12. Polyelectrolyte Complex Based Interfacial Drug Delivery System with Controlled Loading and Improved Release Performance for Bone Therapeutics

    Directory of Open Access Journals (Sweden)

    David Vehlow

    2016-03-01

    Full Text Available An improved interfacial drug delivery system (DDS based on polyelectrolyte complex (PEC coatings with controlled drug loading and improved release performance was elaborated. The cationic homopolypeptide poly(l-lysine (PLL was complexed with a mixture of two cellulose sulfates (CS of low and high degree of substitution, so that the CS and PLL solution have around equal molar charged units. As drugs the antibiotic rifampicin (RIF and the bisphosphonate risedronate (RIS were integrated. As an important advantage over previous PEC systems this one can be centrifuged, the supernatant discarded, the dense pellet phase (coacervate separated, and again redispersed in fresh water phase. This behavior has three benefits: (i Access to the loading capacity of the drug, since the concentration of the free drug can be measured by spectroscopy; (ii lower initial burst and higher residual amount of drug due to removal of unbound drug and (iii complete adhesive stability due to the removal of polyelectrolytes (PEL excess component. It was found that the pH value and ionic strength strongly affected drug content and release of RIS and RIF. At the clinically relevant implant material (Ti40Nb similar PEC adhesive and drug release properties compared to the model substrate were found. Unloaded PEC coatings at Ti40Nb showed a similar number and morphology of above cultivated human mesenchymal stem cells (hMSC compared to uncoated Ti40Nb and resulted in considerable production of bone mineral. RIS loaded PEC coatings showed similar effects after 24 h but resulted in reduced number and unhealthy appearance of hMSC after 48 h due to cell toxicity of RIS.

  13. Polymer electrolyte membranes from fluorinated polyisoprene-block-sulfonated polystyrene: Microdomain orientation by external field

    Energy Technology Data Exchange (ETDEWEB)

    Sodeye, Akinbode [Department of Polymer Science and Engineering, University of Massachusetts; Huang, Tianzi [University of Tennessee, Knoxville (UTK); Gido, Samuel [University of Massachusetts, Amherst; Mays, Jimmy [ORNL

    2011-01-01

    In this study, block copolymer ionomers of the cesium salt (20 mol %) of fluorinated polyisoprene-blocksulfonated polystyrene were spin cast into membranes and annealed under an electric field ofw40 V/mm at 130 C for 24 h. The effect of this treatment was a 2.5 times increase in the ionic conductivity as measured by electrochemical impedance spectroscopy, under all humidity conditions measured. This can be attributed to the increased connectivity of the ionic domains of the block copolymers. This E-field alignment technique may thus find application in the fabrication of nanostructured polyelectrolytes with enhanced charge transport capacity.

  14. Stability of polyelectrolyte-coated iron nanoparticles for T2-weighted magnetic resonance imaging

    Science.gov (United States)

    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.

  15. Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zielińska, Katarzyna, E-mail: kzielinska@gmail.com; Leeuwen, Herman P. van

    2014-09-24

    Highlights: • For the first time SPME fiber is coated with polyelectrolyte layer. • Sorption of nanoparticles on the solid phase surface is prevented. • Polyelectrolyte-modified fiber enables extraction of free analyte in presence of sorbing nanoparticles. - Abstract: In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of poly(diallyldimethylammonium chloride), and poly(sodium 4-styrenesulfonate). The modified fiber provides reproducible, convenient and fast extraction capabilities toward the model analyte, triclosan (TCS). A negatively charged polyelectrolyte coating prevents sorbing oxidic nanoparticles from both partitioning into the PDMS phase and aggregation at its surface. The results for the TCS/nanoparticle sample show that the polyelectrolyte layer-modified solid phase extracts just the free form of the organic compound and enables dynamic speciation analysis of the nanoparticulate target analyte complex.

  16. The experimental study of polyelectrolyte coatings suitability for encapsulation of cells.

    Science.gov (United States)

    Granicka, L H; Antosiak-Iwańska, M; Godlewska, E; Hoser, G; Strawski, M; Szklarczyk, M; Dudziński, K

    2009-01-01

    Living cells encapsulated in polymeric shells are receiving increasing attention because of their possible biotechnological and biomedical applications. The aim of this work is to evaluate how different polyelectrolyte coatings, characterized by different numbers of polyelectrolyte layers and by different polyelectrolyte conformations, affect the viability of encapsulated biological material. We demonstrate the ability to individually encapsulate HL-60 cells as well as rat pancreatic islets within polymeric shells consisting of different PE layers using the layer-by-layer process. Coating of HL-60 cells allows for surviving and functioning of cells for all applied PE as well as for different numbers of layers. The islets encapsulated in applied polyelectrolytes exhibited the lower level of mitochondrial activity as compared to non-encapsulated islets. Nevertheless, encapsulated islets exhibited comparable absorbance values during the whole period of culture. Polyelectrolyte coating seems to be a promising way of allowing capsule void volume minimization in a model of encapsulated biological material for local production of biologically active substances.

  17. Alternate drop coating for forming dual biointerfaces composed of polyelectrolyte multilayers.

    Science.gov (United States)

    Watanabe, Junji; Shen, Heyun; Akashi, Mitsuru

    2009-03-01

    Two types of polyelectrolyte multilayers were formed on both sides of a quartz crystal microbalance (QCM) substrate by a novel alternate drop coating process. In this study, poly(diallyldimethylammonium chloride) (PDDA) and poly(sodium 4-styrene sulfonate) (PSS) were used as strong-strong polyelectrolytes. On the other hand, PDDA and poly(acrylic acid) (PAA) were used as strong-weak polyelectrolytes. The novel alternate drop coating process can separately fabricate each polyelectrolyte multilayer on both sides of the substrate. The substrate provides dual biointerfaces, both sides of which comprise different multilayers, by employing a combination of polymers. The formation of the multilayer by alternate drop coating was evaluated in terms of changes in the frequency of the QCM and model protein adsorption for proteins such as bovine serum albumin, and their characteristics were investigated with those of the conventional alternate adsorption process by performing dip coating. There was no significant difference between the surface properties resulting from the two formation conditions. This result strongly supported the fact that the multilayers fabricated by alternate drop coating were similar in quality to those fabricated by conventional dip coating. The resulting dual biointerfaces with polyelectrolyte multilayers provide alternative biofunctions in terms of individual protein loading. In summary, the novel alternate drop coating process for substrates is a good candidate for the preparation of dual biointerfaces in the biomedical field.

  18. Physico-mechanical analysis data in support of compatibility of chitosan/κ-carrageenan polyelectrolyte films achieved by ascorbic acid, and the thermal degradation theory of κ-carrageenan influencing the properties of its blends

    Directory of Open Access Journals (Sweden)

    Mahdiyar Shahbazi

    2016-12-01

    Full Text Available This article presents the complementary data regarding compatibilization of chitosan/κ-carrageenan polyelectrolyte complex for synthesizing of a soft film using ascorbic acid. It includes the thermal-theory for estimating the degradation of κ-carrageenan, as reflected in alteration of the structural properties of the blend. The data has been provided to demonstrate that the blend solution based on chitosan, a polycation, and κ-carrageenan, a polyanion polymer, produces an incompatible polyelectrolyte composite, susceptible to coaservative phase separation. We present further data on water resistance, water barrier property, mechanical parameters, scanning electron micrograph, as well as contact angle image dataset of the chitosan/κ-carrageenan film. The physical data were collected by water solubility and water permeability assays, with a view to elucidate the role of ascorbic acid in the compatibility of polyelectrolyte blends. The mechanical data is obtained from a stress–strain curve for evaluation of tensile strength and elongation at break point of the chitosan/κ-carrageenan film. The microstructure observations were performed using scanning electron micrograph. These dataset confirm fabrication of a soft film in the presence of ascorbic acid, with reduced heterogeneities in the polyelectrolyte film structure. The κ-carrageenan was also treated by a thermal process, prior to inclusion into the chitosan solution, to investigate the impact of this on the mechanical and structural features of the resulting blend. We present the required data and the theoretical analysis supporting the thermal chain degradation of a polymer and its effects on behavior of the film. Additional information, characterizing the hydrophobicity of the surface of the blend layers is obtained by measuring water contact angles using a contact anglemeter.

  19. Physico-mechanical analysis data in support of compatibility of chitosan/κ-carrageenan polyelectrolyte films achieved by ascorbic acid, and the thermal degradation theory of κ-carrageenan influencing the properties of its blends.

    Science.gov (United States)

    Shahbazi, Mahdiyar; Ettelaie, Rammile; Rajabzadeh, Ghadir

    2016-12-01

    This article presents the complementary data regarding compatibilization of chitosan/κ-carrageenan polyelectrolyte complex for synthesizing of a soft film using ascorbic acid. It includes the thermal-theory for estimating the degradation of κ-carrageenan, as reflected in alteration of the structural properties of the blend. The data has been provided to demonstrate that the blend solution based on chitosan, a polycation, and κ-carrageenan, a polyanion polymer, produces an incompatible polyelectrolyte composite, susceptible to coaservative phase separation. We present further data on water resistance, water barrier property, mechanical parameters, scanning electron micrograph, as well as contact angle image dataset of the chitosan/κ-carrageenan film. The physical data were collected by water solubility and water permeability assays, with a view to elucidate the role of ascorbic acid in the compatibility of polyelectrolyte blends. The mechanical data is obtained from a stress-strain curve for evaluation of tensile strength and elongation at break point of the chitosan/κ-carrageenan film. The microstructure observations were performed using scanning electron micrograph. These dataset confirm fabrication of a soft film in the presence of ascorbic acid, with reduced heterogeneities in the polyelectrolyte film structure. The κ-carrageenan was also treated by a thermal process, prior to inclusion into the chitosan solution, to investigate the impact of this on the mechanical and structural features of the resulting blend. We present the required data and the theoretical analysis supporting the thermal chain degradation of a polymer and its effects on behavior of the film. Additional information, characterizing the hydrophobicity of the surface of the blend layers is obtained by measuring water contact angles using a contact anglemeter.

  20. Polyelectrolyte Layer-by-Layer Assembly on Organic Electrochemical Transistors.

    Science.gov (United States)

    Pappa, Anna-Maria; Inal, Sahika; Roy, Kirsty; Zhang, Yi; Pitsalidis, Charalampos; Hama, Adel; Pas, Jolien; Malliaras, George G; Owens, Roisin M

    2017-03-29

    Oppositely charged polyelectrolyte multilayers (PEMs) were built up in a layer-by-layer (LbL) assembly on top of the conducting polymer channel of an organic electrochemical transistor (OECT), aiming to combine the advantages of well-established PEMs with a high performance electronic transducer. The multilayered film is a model system to investigate the impact of biofunctionalization on the operation of OECTs comprising a poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) film as the electrically active layer. Understanding the mechanism of ion injection into the channel that is in direct contact with charged polymer films provides useful insights for novel biosensing applications such as nucleic acid sensing. Moreover, LbL is demonstrated to be a versatile electrode modification tool enabling tailored surface features in terms of thickness, softness, roughness, and charge. LbL assemblies built up on top of conducting polymers will aid the design of new bioelectronic platforms for drug delivery, tissue engineering, and medical diagnostics.

  1. Characterization of novel lactoferrin loaded capsules prepared with polyelectrolyte complexes.

    Science.gov (United States)

    Wu, Qing-Xi; Zhang, Qi-Lei; Lin, Dong-Qiang; Yao, Shan-Jing

    2013-10-15

    Novel capsules loaded with lactoferrin (LF) were prepared using polyelectrolyte complexes that were formed by water soluble chitosan (WSC), sodium cellulose sulfate (NaCS) and sodium polyphosphate (PPS). Normal chitosan (soluble in acidic conditions) was chosen as a control to prepare similar capsules with NaCS and PPS. (1)H NMR and FTIR spectra analysis showed that WSC was in a form of chitosan hydrochloride which can be directly dissolved and protonated in acid-free water. SEM results showed that the capsules had a typical wall-capsule structure with a regular spherical shape and an average diameter of 1.97 mm. TGA studies revealed that the thermal stability of the capsules were enhanced and the moisture content of the drug-free/loaded capsules were 6.3% and 3.2%. SDS-PAGE results showed that the primary structures of the processed LF in the capsules were unchanged. Drug loading (LE%) and encapsulation efficiency (EE%) analysis showed that the capsules had a higher LE% (45.6%) and EE% (70.7%) than that of the control. In vitro release studies showed that the capsules had a regular and sustainable release profiles in simulated colonic fluid. All of these results indicated that the capsules prepared could be used as a candidate protein drug carrier for colon. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Polyelectrolyte Multilayers: A Versatile Tool for Preparing Antimicrobial Coatings.

    Science.gov (United States)

    Séon, Lydie; Lavalle, Philippe; Schaaf, Pierre; Boulmedais, Fouzia

    2015-12-01

    The prevention of pathogen colonization of medical implants represents a major medical and financial issue. The development of antimicrobial coatings aimed at protecting against such infections has thus become a major field of scientific and technological research. Three main strategies are developed to design such coatings: (i) the prevention of microorganisms adhesion and the killing of microorganisms (ii) by contact and (iii) by the release of active compounds in the vicinity of the implant. Polyelectrolyte multilayer (PEM) technology alone covers the entire widespread spectrum of functionalization possibilities. PEMs are obtained through the alternating deposition of polyanions and polycations on a substrate, and the great advantages of PEMs are that (i) they can be applied to almost any type of substrate whatever its shape and composition; (ii) various chemical, physicochemical, and mechanical properties of the coatings can be obtained; and (iii) active compounds can be embedded and released in a controlled manner. In this article we will give an overview of the field of PEMs applied to the design of antimicrobial coatings, illustrating the large versatility of the PEM technology.

  3. Underwater Reversible Adhesion Between Oppositely Charged Weak Polyelectrolytes

    Science.gov (United States)

    Alfhaid, Latifah; Geoghegan, Mark; Williams, Nicholas; Seddon, William

    2015-03-01

    Force-distance data has shown that the adhesion between two oppositely charged polyelectrolytes: poly(methacrylic acid) (PMAA, a polyacid) and poly[2-(diethylamino)ethyl methacrylate] (PDEAEMA, a polybase), was controllable by varying the pH level of their surrounding. Accordingly, adhesive force at the interface between these two polymers was higher inside basic surroundings at pH 6 and 7, and then it started to decrease at pH level below 3 and above 8. Stimulating adhesion between PMAA gel and PDEAEMA brushes by adding salt to their surrounded water has only a limited effect on the adhesive force between them, contradicting previous results. Increasing the molar concentration of sodium chloride (NaCl) in the surrounded water of these two polymers from 0.1 to 1M did not decrease the adhesion forces between a PMAA gel and a grafted PDEAEMA layer (brush). The JKR equation was used to evaluate the adhesion forces between the polymer gel and the brushes and it was observed that the adhesion increased with the elastic modulus of the gel decreased.

  4. Polyelectrolyte Layer-by-Layer Assembly on Organic Electrochemical Transistors

    KAUST Repository

    Pappa, Anna-Maria

    2017-03-06

    Oppositely charged polyelectrolyte multilayers (PEMs) were built up in a layer-by-layer (LbL) assembly on top of the conducting polymer channel of an organic electrochemical transistor (OECT), aiming to combine the advantages of well-established PEMs with a high performance electronic transducer. The multilayered film is a model system to investigate the impact of biofunctionalization on the operation of OECTs comprising a poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) film as the electrically active layer. Understanding the mechanism of ion injection into the channel that is in direct contact with charged polymer films provides useful insights for novel biosensing applications such as nucleic acid sensing. Moreover, LbL is demonstrated to be a versatile electrode modification tool enabling tailored surface features in terms of thickness, softness, roughness, and charge. LbL assemblies built up on top of conducting polymers will aid the design of new bioelectronic platforms for drug delivery, tissue engineering, and medical diagnostics.

  5. Fibers by interfacial polyelectrolyte complexation – processes, materials and applications

    Directory of Open Access Journals (Sweden)

    Andrew C.A. Wan

    2016-10-01

    Full Text Available Interfacial polyelectrolyte (polyion complexation (IPC is a process whereby fibers and capsules are formed through interactions at the interface of oppositely charged polymers. Since its discovery in the late 1990s, the IPC fiber process, in particular, has been investigated for various applications such as tissue engineering, drug delivery, flexible electronics and biosensing. The advent of the IPC fiber and process has been supported by its unique mechanism of formation that makes it amenable to encapsulation and functionalization. In this first review on IPC fibers, we consolidate the current knowledge of the IPC process, mechanism of fiber formation and fiber physical properties, while documenting the various polycation–polyanion pairs and encapsulants that have been used to date. We review the rapidly accumulating literature on IPC fibers for tissue engineering, describing how they have been used to release protein factors in a sustained manner, made into random or spatially well-defined scaffolds and decorated with appropriate functionalities and extracellular matrices in order to tailor the microenvironment for cell growth and function.

  6. Preparation of photoluminescent carbon dots-embedded polyelectrolyte microcapsules

    Institute of Scientific and Technical Information of China (English)

    Xiaoling Yang; Liming Peng; Jie Zong; Yihua Zhu

    2013-01-01

    Two types of photoluminescent carbon dots (CDs)-embedded polyelectrolyte (PE) microcapsules were successfully prepared via the layer-by-layer (LbL) assembly approach on sacrificial templates.For the first type,the PE microcapsules with CDs embedded in the cavity were produced from assembly of five pairs of poly(sodium 4-styrensulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) on CDs-pre-loaded meso-porous silica.For the second type,the PE microcapsules with CDs embedded in the wall were made of CDs and PAH,which were derived from SiO2 particles as templates.Microscope images confirmed the introduction of CDs into the two CDs-embedded microcapsules.These two microcapsules also retained the optical properties of free CDs.Photoluminescence spectra revealed that the two types of microcapsules had excitation-dependent photoluminescence behavior.When the excitation wavelength changed from 280 to 340 nm,photoluminescence emission peak of the PE microcapsules with CDs embedded in the cavity shifts from 369 to 377 nm,while for microcapsules with CDs embedded in the wall,emission peak shifts from 367 to 390 nm.Due to low toxicity,good hydrophilicity and photoluminescence properties of CDs,these two kinds of photo-luminescent microcapsules have competitive potential for application in carriers for imaging,drug delivery and biosensors.

  7. Effect of Temperature on Polyelectrolyte Expansion of Lignosulfonate

    Directory of Open Access Journals (Sweden)

    Hao Li

    2014-11-01

    Full Text Available The temperature effect on the polyelectrolyte expansion of sodium lignosulfonate (SL was studied in the range of 20 to 38 °C. A narrow molecular-weight distribution fraction of sodium lignosulfonate was first obtained by gel column chromatography, which was suitable for the hydrodynamic radius (Rh measurement by dynamic light scattering (DLS. Dynamic light scattering experiments showed that the hydrodynamic radius of sodium lignosulfonate decreased with increasing temperature. Using a quartz crystal microbalance (QCM and atomic force microscopy (AFM, it was found that the adsorbed sodium lignosulfonate film lost water with increasing temperature and reabsorbed water with decreasing temperature. Surface tension and contact angle experiments showed that there were more hydrophobic groups on the surface of the sodium lignosulfonate molecule as the temperature increased. It can be concluded that the sodium lignosulfonate molecule shrank and became more hydrophobic with increasing temperature. Analysis suggests that the decreasing of the hydrogen-bond interactions between the sodium lignosulfonate molecule and water molecules with increasing temperature is the primary reason for the molecular conformation change of sodium lignosulfonate.

  8. Mutable polyelectrolyte tube arrays: mesoscale modeling and lateral force microscopy.

    Science.gov (United States)

    Cranford, Steven W; Han, Lin; Ortiz, Christine; Buehler, Markus J

    2017-08-23

    In this study, the pH-dependent friction of layer-by-layer assemblies of poly(allylamine hydrochloride) and poly(acrylic acid) (PAH/PAA) are quantified for microtube array structures via experimental and simulated lateral force microscopy (LFM). A novel coarse-grain tube model is developed, utilizing a molecular dynamics (MD) framework with a Hertzian soft contact potential (such that F ∼ δ(3/2)) to allow the efficient dynamic simulation of 3D arrays consisting of hundreds of tubes at micrometer length scales. By quantitatively comparing experimental LFM and computational results, the coupling between geometry (tube spacing and swelling) and material properties (intrinsic stiffness) results in a transition from bending dominated deformation to bending combined with inter-tube contact, independent of material adhesion assumptions. Variation of tube spacing (and thus control of contact) can be used to exploit the normal and lateral resistance of the tube arrays as a function of pH (2.0/5.5), beyond the effect of areal tube density, with increased resistances (potential mutability) up to a factor of ∼60. This study provides a novel modeling platform to assess and design dynamic polyelectrolyte-based substrates/coatings with tailorable stimulus-responsive surface friction. Our results show that micro-geometry can be used alongside stimulus-responsive material changes to amplify and systematically tune mutability.

  9. Polyelectrolyte coating of ferumoxytol nanoparticles for labeling of dendritic cells

    Energy Technology Data Exchange (ETDEWEB)

    Celikkin, Nehar; Jakubcová, Lucie; Zenke, Martin [Institute for Biomedical Engineering, Department of Cell Biology, RWTH Aachen University Hospital, Pauwelsstrasse 30, 52074 Aachen (Germany); Helmholtz Institute for Biomedical Engineering, RWTH Aachen University, Pauwelsstrasse 20, 52074 Aachen (Germany); Hoss, Mareike [Institute of Pathology, Electron Microscopy Facility, RWTH Aachen University Hospital, Pauwelsstrasse 30, 52074 Aachen (Germany); Wong, John Erik, E-mail: John.Wong@avt.rwth-aachen.de [Chemical Process Engineering, RWTH Aachen University, Turmstrasse 46, 52056 Aachen (Germany); DWI – Leibniz Institute for Interactive Materials Research, Forckenbeckstrasse 50, Aachen (Germany); Hieronymus, Thomas, E-mail: thomas.hieronymus@rwth-aachen.de [Institute for Biomedical Engineering, Department of Cell Biology, RWTH Aachen University Hospital, Pauwelsstrasse 30, 52074 Aachen (Germany); Helmholtz Institute for Biomedical Engineering, RWTH Aachen University, Pauwelsstrasse 20, 52074 Aachen (Germany)

    2015-04-15

    Engineered magnetic nanoparticles (MNPs) are emerging to be used as cell tracers, drug delivery vehicles, and contrast agents for magnetic resonance imaging (MRI) for enhanced theragnostic applications in biomedicine. In vitro labeling of target cell populations with MNPs and their implantation into animal models and patients shows promising outcomes in monitoring successful cell engraftment, differentiation and migration by using MRI. Dendritic cells (DCs) are professional antigen-presenting cells that initiate adaptive immune responses. Thus, DCs have been the focus of cellular immunotherapy and are increasingly applied in clinical trials. Here, we addressed the coating of different polyelectrolytes (PE) around ferumoxytol particles using the layer-by-layer technique. The impact of PE-coated ferumoxytol particles for labeling of DCs and Flt3{sup +} DC progenitors was then investigated. The results from our studies revealed that PE-coated ferumoxytol particles can be readily employed for labeling of DC and DC progenitors and thus are potentially suitable as contrast agents for MRI tracking.

  10. Effect of bovine serum albumin on the micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solutions by fluorescence spectroscopy

    Institute of Scientific and Technical Information of China (English)

    GUO Chen; WANG Jing; LIANG Xiangfeng; ZHENG Lili; LIU Huizhou

    2006-01-01

    Effect of bovine serum albumin (BSA) on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers was investigated using pyrene fluorescence spectroscopy. The critical micellization temperature (CMT) of pluronics in aqueous solution was increased by the addition of BSA. A closed association model was used to obtain the standard free energies (△G0), enthalpies (△H 0), and entropies (△S0) of micellization. The standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA content. The more PPO component in the pluronic polymer, the higher the changed values of micellization enthalpy and entropy. The hydrophobic part of the pluronics, PPO, was responsible for the interaction between pluronics and BSA. Hydrophobic interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA, which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.

  11. Recent Progress and Perspectives in the Electrokinetic Characterization of Polyelectrolyte Films

    Directory of Open Access Journals (Sweden)

    Ralf Zimmermann

    2015-12-01

    Full Text Available The analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there has been significant progress in the quantitative interpretation of streaming current and surface conductivity data of polymeric films from the application of recent theories developed for the electrohydrodynamics of diffuse soft planar interfaces. Here, we review the theory and experimental strategies to analyze the interrelations of the charge and structure of polyelectrolyte layers supported by planar carriers under electrokinetic conditions. To illustrate the options arising from these developments, we discuss experimental and simulation data for plasma-immobilized poly(acrylic acid films and for a polyelectrolyte bilayer consisting of poly(ethylene imine and poly(acrylic acid. Finally, we briefly outline potential future developments in the field of the electrokinetics of polyelectrolyte layers.

  12. Treatment of effluents of poultry slaughterhouse with aluminum salts and natural polyelectrolytes.

    Science.gov (United States)

    Ikeda, E; Rodrigues, D G; Nozaki, J

    2002-08-01

    A mixture of aluminum salts and natural polyelectrolytes, extracted from the cactus Opuntia ficus indica, has been used for cleaning of wastewater from poultry slaughterhouse. The aggregation and settling properties of colloids and complex organics such as oil, grease, fats, proteins, and suspended solids, was increased if compared with conventional methods of wastewater treatment using only aluminum or iron sulfate. A mixture of aluminum salt in a concentration range of 300 to 600 mg l(-1) and natural polyelectrolytes of 0.6 to 0.8 mg l(-1) was used for flocculation and coagulation. The combination of coagulant and natural polyelectrolytes was able to remove chemical oxygen demand (86%), oil and grease (93%), turbidity (89%), and suspended solids (93%). Methanization activity was also investigated for the effluents in natura.

  13. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    Science.gov (United States)

    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

  14. Synthesis and characterization of CdS-polyelectrolyte-Bi2S3 thin film by SILAR

    Science.gov (United States)

    Desale, Dipalee J.; Shaikh, Shaheed; Siddiqui, Farha; AnilGhule, Ravikiran Birajadar; Sharma, Ramphal

    2012-06-01

    CdS-Polyelectrolyte-Bi2S3 was grown by cost effective successive ionic layer adsorption and reaction method (SILAR) on glass substrate. The polyelectrolyte used as a protecting layer for excessive ionic loss during the exchange reaction between the cation and anions of the reactants. Thin films was characterized for structural, morphological and an I-V characteristic. The X-ray diffraction pattern (XRD) pattern shows that, CdS-Polyelectrolyte-Bi2S3 thin films have mixed phase of hexagonal and orthorhombic crystal structures corresponding to CdS and Bi2S3 respectively. Scanning electron microscopy (SEM) corresponds deposition of the material along with the presence of bundle like shape is observed in thin film. The I-V measurement under dark and illumination to 100 mW/cm2 shows increase in photoconductivity.

  15. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets.

    Science.gov (United States)

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M; Ye, Mingxin

    2016-05-01

    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems.

  16. Flexible polyelectrolyte conformation in the presence of cationic and anionic surfactants

    Science.gov (United States)

    Passos, C. B.; Kuhn, P. S.; Diehl, A.

    2015-11-01

    In this work we have studied the conformation of flexible polyelectrolyte chains in the presence of cationic and anionic surfactant molecules. We developed a simple theoretical model for the formation of the polyelectrolyte-cationic surfactant complexes and mixed micelles formed by cationic and anionic surfactant molecules, in the framework of the Debye-Hückel-Bjerrum-Manning and Flory theories, with the hydrophobic interaction included explicitly as an effective short-ranged attraction between the surfactant hydrocarbon tails. This simple model allows us to calculate the extension of the polyelectrolyte-cationic surfactant complexes as a function of the anionic surfactant concentration, for different types of cationic and anionic surfactant molecules. A discrete conformational transition from a collapsed state to an elongated coil was found, for all surfactant chain lengths we have considered, in agreement with the experimental observations for the unfolding of ​DNA-cationic surfactant complexes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Pryamitsyn, Victor [Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712 (United States); Ganesan, Venkat, E-mail: venkat@che.utexas.edu [Department of Chemical Engineering and Institute for Computational and Engineering Sciences, University of Texas at Austin, Austin, Texas 78712 (United States)

    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.

  18. Generation of mechanical force by grafted polyelectrolytes in an electric field: application to polyelectrolyte-based nano-devices

    Science.gov (United States)

    Brilliantov, N. V.; Budkov, Yu. A.; Seidel, C.

    2016-11-01

    We analyse theoretically and by means of molecular dynamics (MD) simulations the generation of mechanical force by a polyelectrolyte (PE) chain grafted to a plane. The PE is exposed to an external electric field that favours its adsorption on the plane. The free end of the chain is linked to a deformable target body. By varying the field, one can alter the length of the non-adsorbed part of the chain. This entails variation of the deformation of the target body and hence variation of the force arising in the body. Our theoretical predictions for the generated force are in very good agreement with the MD data. Using the theory developed for the generated force, we study the effectiveness of possible PE-based nano-vices, composed of two clenching planes connected by PEs and exposed to an external electric field. We exploit the Cundall-Strack solid friction model to describe the friction between a particle and the clenching planes. We compute the diffusion coefficient of a clenched particle and show that it drastically decreases even in weak applied fields. This demonstrates the efficacy of the PE-based nano-vices, which may be a possible alternative to the existing nanotube nano-tweezers and optical tweezers. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  19. Structure-property relationships in the design, assembly and applications of polyelectrolyte multilayer thin films

    Science.gov (United States)

    Rmaile, Hassan H.

    Ultrathin films consisting of an alternating sequence of positively and negatively charged polyelectrolytes have been prepared by means of the electrostatic layer-by-layer sequential assembly technique. To augment their typical applications in the water treatment, personal care as well as the pulp and paper industry, the structure and the design of these polyelectrolytes were tailored synthetically to satisfy the requirements of different types of applications. Some were used for surface modifications, hydrophobic and hydrophilic coatings, corrosion protection, conducting and biocompatible surfaces. Others were found to be very efficient for membrane and chromatographic applications. The ease with which these multilayer coatings can be constructed, their robustness and stability make them very good candidates for industrial applications. The dissertation focuses mainly on the structure-property relationships of these polyelectrolytes and their corresponding thin films. Various polyelectrolytes were synthesized or modified in a strategic approach and gave novel and promising properties. Some of them exhibited permeabilities that were higher than any membranes reported in the literature. Also, some are potentially very useful for designing drug delivery systems such as tablets or encapsulations since they were shown to control the permeability of sample drugs and vitamins very efficiently based on their sensitivity to pH changes. Other synthesized polyelectrolytes proved to be very effective in preventing protein adsorption or promoting cell growth and differentiation. Some systems were very useful as robust stationary phases for simple chiral separations in capillary electrochromatography. Along with modifications and improvements, the approach might one day be applied commercially for chiral separations using high performance liquid chromatography and replace currently used stationary phases. Last but not least, the potential for these polyelectrolytes and their

  20. Composite scaffold of poly(vinyl alcohol) and interfacial polyelectrolyte complexation fibers for controlled biomolecule delivery.

    Science.gov (United States)

    Cutiongco, Marie Francene A; Choo, Royden K T; Shen, Nathaniel J X; Chua, Bryan M X; Sju, Ervi; Choo, Amanda W L; Le Visage, Catherine; Yim, Evelyn K F

    2015-01-01

    Controlled delivery of hydrophilic proteins is an important therapeutic strategy. However, widely used methods for protein delivery suffer from low incorporation efficiency and loss of bioactivity. The versatile interfacial polyelectrolyte complexation (IPC) fibers have the capacity for precise spatiotemporal release and protection of protein, growth factor, and cell bioactivity. Yet its weak mechanical properties limit its application and translation into a viable clinical solution. To overcome this limitation, IPC fibers can be incorporated into polymeric scaffolds such as the biocompatible poly(vinyl alcohol) hydrogel (PVA). Therefore, we explored the use of a composite scaffold of PVA and IPC fibers for controlled biomolecule release. We first observed that the permeability of biomolecules through PVA films were dependent on molecular weight. Next, IPC fibers were incorporated in between layers of PVA to produce PVA-IPC composite scaffolds with different IPC fiber orientation. The composite scaffold demonstrated excellent mechanical properties and efficient biomolecule incorporation. The rate of biomolecule release from PVA-IPC composite grafts exhibited dependence on molecular weight, with lysozyme showing near-linear release for 1 month. Angiogenic factors were also incorporated into the PVA-IPC grafts, as a potential biomedical application of the composite graft. While vascular endothelial growth factor only showed a maximum cumulative release of 3%, the smaller PEGylated-QK peptide showed maximum release of 33%. Notably, the released angiogenic biomolecules induced endothelial cell activity thus indicating retention of bioactivity. We also observed lack of significant macrophage response against PVA-IPC grafts in a rabbit model. Showing permeability, mechanical strength, precise temporal growth factor release, and bioinertness, PVA-IPC fibers composite scaffolds are excellent scaffolds for controlled biomolecule delivery in soft tissue engineering.

  1. Effect of cationic polyelectrolytes on the performance of paper diagnostics for blood typing.

    Science.gov (United States)

    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.

  2. Composite scaffold of poly(vinyl alcohol and interfacial polyelectrolyte complexation fibers for controlled biomolecule delivery

    Directory of Open Access Journals (Sweden)

    Marie Francene Arnobit Cutiongco

    2015-02-01

    Full Text Available Controlled delivery of hydrophilic proteins is an important therapeutic strategy. However, widely used methods for protein delivery suffer from low incorporation efficiency and loss of bioactivity. The versatile interfacial polyelectrolyte complexation (IPC fibers have the capacity for precise spatiotemporal release and protection of protein, growth factor and cell bioactivity. Yet its weak mechanical properties limit its application and translation into a viable clinical solution. To overcome this limitation, IPC fibers can be incorporated into polymeric scaffolds such as the biocompatible poly(vinyl alcohol hydrogel (PVA. Therefore, we explored the use of a composite scaffold of PVA and IPC fibers for controlled biomolecule release. We first observed that the permeability of biomolecules through PVA films were dependent on molecular weight, with lysozyme showing near-linear release for 1 month. Next, IPC fibers were incorporated in between layers of PVA to produce PVA-IPC composite scaffolds with different IPC fiber orientation. The composite scaffold demonstrated excellent mechanical properties and efficient biomolecule incorporation. The rate of biomolecule release from PVA-IPC composite grafts exhibited dependence on molecular weight. Angiogenic factors were also incorporated into the PVA-IPC grafts, as a potential biomedical application of the composite graft. While vascular endothelial growth factor only showed a maximum cumulative release of 3%, the smaller PEGylated-QK peptide showed maximum release of 33%. Notably, the released angiogenic biomolecules induced endothelial cell metabolic activity thus indicating retention of bioactivity. We also observed lack of significant macrophage response against PVA-IPC grafts in a rabbit model. Showing permeability, mechanical strength, precise temporal growth factor release and bioinertness, PVA-IPC fibers composite scaffolds are excellent scaffolds for controlled biomolecule delivery in soft

  3. Polyacrylonitrile nanofiber membranes modified with ionically crosslinked polyelectrolyte multilayers for the separation of ionic impurities.

    Science.gov (United States)

    Rajesh, Sahadevan; Zhao, Yong; Fong, Hao; Menkhaus, Todd J

    2016-11-03

    Nanofiltration membranes were prepared by forming multilayers of branched polyethylenimine (BPEI) and polyacrylic acid (PAA) on a polyacrylonitrile (PAN) nanofibrous mat by layer-by-layer (LbL) assembly. The degree of ionization (DI) of PAA, estimated using FTIR spectra both in the absence and presence of added salt, was shown to have a strong influence on the BPEI/PAA film growth. BPEI/PAA multilayers grew exponentially when the DI of PAA was less than 30%, or when the pH of PAA during LbL formation was less than 3.5. Subsequently, BPEI/PAA multilayers were formed on the PAN nanofiber mats by depositing the polyelectrolytes at the experimental conditions that favored maximum film growth. The separation layer formed with 15 bilayers of BPEI/PAA has a thickness of 1100 nm. PAA ionization was favored within the BPEI/PAA multilayers due to the presence of abundant amine groups in BPEI, and as a result, a strong negative charge was seen for PAN nanofibrous membranes for solution conditions above pH 4.5. Nanofiber membranes modified with 15 bilayers of BPEI/PAA multilayers at an applied pressure of 4 bar had a pure water flux of 19.7 Lm(-2) h(-1) and a MgSO4 rejection of 98.7%. This performance represents 1.6 times higher flux and 1.1 times higher salt rejection than the multilayers formed on a conventional asymmetric polymeric support. The higher separation and higher flux capabilities of BPEI/PAA multilayer modified PAN nanofiber membranes was due to the combined effect of high charge density and high porosity of the nanofiber membranes.

  4. Introducing a high gravity field to enhance infiltration of small molecules into polyelectrolyte multilayers.

    Science.gov (United States)

    Liu, Xiaolin; Zhao, Kun; Jiang, Chao; Wang, Yue; Shao, Lei; Zhang, Yajun; Shi, Feng

    2015-07-28

    Loading functional small molecules into nano-thin films is fundamental to various research fields such as membrane separation, molecular imprinting, interfacial reaction, drug delivery etc. Currently, a general demand for enhancing the loading rate without affecting the film structures exists in most infiltration phenomena. To handle this issue, we have introduced a process intensification method of a high gravity technique, which is a versatile energy form of mechanical field well-established in industry, into the investigations on diffusion/infiltration at the molecular level. By taking a polyelectrolyte multilayer as a model thin film and a photo-reactive molecule, 4,4'-diazostilbene-2,2'-disulfonic acid disodium salt (DAS), as a model small functional molecule, we have demonstrated remarkably accelerated adsorption/infiltration of DAS into a poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) multilayer by as high as 20-fold; meanwhile, both the film property of the multilayer and photoresponsive-crosslinking function of DAS were not disturbed. Furthermore, the infiltration of DAS and the surface morphology of the multilayer could be tuned based on their high dependence on the intensity of the high gravity field regarding different rotating speeds. The mechanism of the accelerated adsorption/infiltration under the high gravity field was interpreted by the increased turbulence of the diffusing layer with the thinned laminar boundary layer and the stepwise delivery of the local concentration gradient from the solution to the interior of the multilayer. The introduction of mechanical field provides a simple and versatile strategy to address the paradox of the contradictory loading amount and loading rate, and thus to promote applications of various membrane processes.

  5. Facile preparation of cobaltocenium-containing polyelectrolyte via click chemistry and RAFT polymerization.

    Science.gov (United States)

    Yan, Yi; Zhang, Jiuyang; Qiao, Yali; Tang, Chuanbing

    2014-01-01

    A facile method to prepare cationic cobaltocenium-containing polyelectrolyte is reported. Cobaltocenium monomer with methacrylate is synthesized by copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction between 2-azidoethyl methacrylate and ethynylcobaltocenium hexafluorophosphate. Further controlled polymerization is achieved by reversible addition-fragmentation chain transfer polymerization (RAFT) by using cumyl dithiobenzoate (CDB) as a chain transfer agent. Kinetic study demonstrates the controlled/living process of polymerization. The obtained side-chain cobaltocenium-containing polymer is a metal-containing polyelectrolyte that shows characteristic redox behavior of cobaltocenium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Biofunctionalization of polyelectrolyte microcapsules with biotinylated polyethylene glycol-grafted liposomes.

    Science.gov (United States)

    Gao, Jie; Reibetanz, Uta; Venkatraman, Subbu; Neu, Björn

    2011-08-11

    Hollow polyelectrolyte microcapsules (PEMC) are prepared using layer-by-layer self-assembly of polyelectrolytes on melamine formaldehyde templates, followed by template dissolution, and subsequent coating with biotinylated polyethylene glycol-grafted liposomes. These potential site-specific carrier systems show a high specificity for NeutrAvidin binding and a strong resistance against unspecific protein binding. It is concluded that this design with NeutrAvidin as the outermost layer of such capsules provides an ideal platform for the biofunctionalization of PEMC as drug delivery systems or as artificial cell-like structures for biomimetic studies.

  7. Multiple internalization pathways of polyelectrolyte multilayer capsules into mammalian cells.

    Science.gov (United States)

    Kastl, Lena; Sasse, Daniel; Wulf, Verena; Hartmann, Raimo; Mircheski, Josif; Ranke, Christiane; Carregal-Romero, Susana; Martínez-López, José Antonio; Fernández-Chacón, Rafael; Parak, Wolfgang J; Elsasser, Hans-Peter; Rivera Gil, Pilar

    2013-08-27

    Polyelectrolyte multilayer (PEM) capsules are carrier vehicles with great potential for biomedical applications. With the future aim of designing biocompatible, effective therapeutic delivery systems (e.g., for cancer), the pathway of internalization (uptake and fate) of PEM capsules was investigated. In particular the following experiments were performed: (i) the study of capsule co-localization with established endocytic markers, (ii) switching-off endocytotic pathways with pharmaceutical/chemical inhibitors, and (iii) characterization and quantification of capsule uptake with confocal and electron microscopy. As result, capsules co-localized with lipid rafts and with phagolysosomes, but not with other endocytic vesicles. Chemical interference of endocytosis with chemical blockers indicated that PEM capsules enter the investigated cell lines through a mechanism slightly sensitive to electrostatic interactions, independent of clathrin and caveolae, and strongly dependent on cholesterol-rich domains and organelle acidification. Microscopic characterization of cells during capsule uptake showed the formation of phagocytic cups (vesicles) to engulf the capsules, an increased number of mitochondria, and a final localization in the perinuclear cytoplasma. Combining all these indicators we conclude that PEM capsule internalization in general occurs as a combination of different sequential mechanisms. Initially, an adsorptive mechanism due to strong electrostatic interactions governs the stabilization of the capsules at the cell surface. Membrane ruffling and filopodia extensions are responsible for capsule engulfing through the formation of a phagocytic cup. Co-localization with lipid raft domains activates the cell to initiate a lipid-raft-mediated macropinocytosis. Internalization vesicles are very acidic and co-localize only with phagolysosome markers, excluding caveolin-mediated pathways and indicating that upon phagocytosis the capsules are sorted to

  8. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Cha, E.H. [The Faculty of Liberal Arts (Chemistry), Hoseo University, Asan Choongnam 336-795 (Korea); Lim, S.A. [Functional Proteomics Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea); Park, J.H. [Department of Herbal Medicine, Hoseo University, Asan Choongnam 336-795 (Korea); Kim, D.W. [Department of Chemical Technology, Han Bat National University, Daejon 305-719 (Korea); Macfarlane, D.R. [School of Chemistry, Monash University, Clayton, Vic. 3800 (Australia)

    2008-04-01

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N,N-dimethyl-N-propyl-N-butyl ammonium tricyanomethanide (N{sub 1134}TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 x 10{sup -3} S cm{sup -1} at 25 C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 x 10{sup -3} S cm{sup -1} at 25 C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N{sub 1134}TCM (2.48 x 10{sup -3} S cm{sup -1}). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N{sub 1134}TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species. (author)

  9. Polyelectrolyte complex/PVA membranes for diffusion dialysis.

    Science.gov (United States)

    Wang, Cong; Wu, Cuiming; Wu, Yonghui; Gu, Jingjing; Xu, Tongwen

    2013-10-15

    Polyelectrolyte complexes (PECs)/polyvinyl alcohol (PVA) membranes are prepared from PVA, anion exchange and cation exchange multisilicon copolymers, which contain plenty of functional groups of OH, N(+)(CH3)3/Si(OCH3)3, and SO3Na/Si(OCH3)3, respectively. The OH and Si(OCH3)3 groups can undertake sol-gel reaction to form crosslinking structure, while the N(+)(CH3)3 and SO3Na groups can be combined through electrostatic interaction. The PECs/PVA membranes exhibit improved thermal stability, swelling resistance and flexibility as compared with single anion or cation exchange hybrid membranes. The PECs/PVA membranes have the water uptakes (WR) of 25.3-70.4%, initial decomposition temperatures (IDTs) of 246-285°C, tensile strength of 23.1-33.8 MPa, and elongation at break of 3.5-13.1%. The membranes can be potentially applied for both acid and alkali recovery through diffusion dialysis (DD) process. The separation factor (S) for HCl/FeCl2 mixture can reach up to 89.9, which is about five times higher than that of commercial DF-120 membrane (18.5 at 25°C). The dialysis coefficients of NaOH (UOH) are in the range of 0.014-0.019 m/h, around 7-9 times higher than the value of commercial SPPO membrane (0.002 m/h at 25°C). The membranes also show potential usefulness for industrial acidic and alkali wastes treatment.

  10. Engineering muscle tissues on microstructured polyelectrolyte multilayer films.

    Science.gov (United States)

    Monge, Claire; Ren, Kefeng; Berton, Kevin; Guillot, Raphael; Peyrade, David; Picart, Catherine

    2012-08-01

    The use of surface coating on biomaterials can render the original substratum with new functionalities that can improve the chemical, physical, and mechanical properties as well as enhance cellular cues such as attachment, proliferation, and differentiation. In this work, we combined biocompatible polydimethylsiloxane (PDMS) with a biomimetic polyelectrolyte multilayer (PEM) film made of poly(L-lysine) and hyaluronic acid (PLL/HA) for skeletal muscle tissue engineering. By microstructuring PDMS in grooves of a different width (5, 10, 30, and 100 μm) and by modulating the stiffness of the (PLL/HA) films, we guided skeletal muscle cell differentiation into myotubes. We found optimal conditions for both the formation of parallel-oriented myotubes and their maturation. Significantly, the myoblasts were collectively prealigned to the grooves before their differentiation. Before fusion, the highest aspect ratio and orientation of nuclei were observed for the 5 and 10 μm wide micropatterns. The formation of myotubes was observed regardless of the size of the micropatterns, and we found that their typical width was 10-12 μm. Their maturation was characterized by the immunolabeling of type II isomyosin. The amount of myosin striation was not affected by the topography, except for the 5 μm wide micropatterns. We highlighted the spatial constraints that led to an important nuclei deformation and further impairment of maturation within the 5 μm grooves. Altogether, our results show that the PEM film combined with PDMS is a powerful tool that is used for skeletal muscle engineering. This work opens perspectives for the development of skeletal muscle tissue in contact with films containing bioactive peptides or growth factors as well as for the study of pathogenic myotubes.

  11. Surface Modification of Multiwall Carbon Nanotubes with Cationic Conjugated Polyelectrolytes: Fundamental Interactions and Intercalation into Conductive Poly(methyl-methacrylate) Composites

    KAUST Repository

    Ezzeddine, Alaa

    2015-05-22

    This research investigates the modification and dispersion and of pristine multiwalled carbon nanotubes (MWCNTs) through a simple solution mixing technique based on noncovalent interactions between poly(phenylene ethynylene) based conjugated polyelectrolytes functionalized with cationic imidazolium solubilizing groups (PIM-2 and PIM-4) and MWCNTs. Spectroscopic studies demonstrated the ability of PIMs to strongly interact with and efficiently disperse MWCNTs in different solvents mainly due to π-interactions between the PIMs and MWCNTs. Transmission electron microscopy and atomic force microscopy revealed the coating of the polyelectrolytes on the walls of the nanotubes. Scanning electron microscopy (SEM) studies confirm the homogenous dispersion of PIM modified MWCNTs in poly(methyl methacrylate) (PMMA) matrix. The addition of 1 wt% PIM modified MWCNTs to the matrix has led to a significant decrease in DC resistivity of the composite (13 orders of magnitude). The increase in electrical conductivity and the improvement in thermal and mechanical properties of the membranes containing the PIM modified MWCNTs is ascribed to the formation of MWCNTs networks and cross-linking sites that provided channels for the electrons to move in throughout the matrix and reinforced the interface between MWCNTs and PMMA.

  12. Phase behavior and molecular thermodynamics of coacervation in oppositely charged polyelectrolyte/surfactant systems: a cationic polymer JR 400 and anionic surfactant SDS mixture.

    Science.gov (United States)

    Li, Dongcui; Kelkar, Manish S; Wagner, Norman J

    2012-07-17

    Coacervation in mixtures of polyelectrolytes and surfactants with opposite charge is common in nature and is also technologically important to consumer health care products. To understand the complexation behavior of these systems better, we combine multiple experimental techniques to systematically study the polymer/surfactant binding interactions and the phase behavior of anionic sodium dodecyl sulfate (SDS) surfactant in cationic JR 400 polymer aqueous solutions. The phase-behavior study resolves a discrepancy in the literature by identifying a metastable phase between the differing redissolution phase boundaries reported in the literature for the surfactant-rich regime. Isothermal titration calorimetry analyzed within the framework of the simple Satake-Yang model identifies binding parameters for the surfactant-lean phase, whereas a calculation for polymer-bound micelles coexisting with free micelles is analyzed in the surfactant-rich redissolution regime. This analysis provides a preliminary understanding of the interactions governing the observed phase behavior. The resulting thermodynamic properties, including binding constants and the molar Gibbs free energies, enthalpies, and entropies, identify the relative importance of both hydrophobic and electrostatic interactions and provide a first approximation for the corresponding microstructures in the different phases. Our study also addresses the stability and metastability of oppositely charged polyelectrolytes and surfactant mixtures.

  13. Thin films of protein (BSA, lysozyme) - Polyelectrolyte (PSS) complexes show larger red-shift in optical emissions irrespective of protein conformation

    Science.gov (United States)

    Talukdar, Hrishikesh; Kundu, Sarathi

    2017-09-01

    Protein-polyelectrolyte complexes (PPC) are prepared using globular proteins (BSA, lysozyme) and optically active polyelectrolyte poly (sodium 4-styrenesulfonate) (PSS) in aqueous solutions and as thin films on solid substrates to explore their structures and optical behaviors. Out-of-plane structures of PPC films having ≈15-60 nm thicknesses are investigated from X-ray reflectivity and their relatively smooth surface morphologies are obtained from atomic force microscopy. ATR-FTIR spectroscopy confirms that the conformation of BSA proteins inside the films of PSSB (PSS+BSA) is nearly same with pure BSA but for lysozyme inside PSSL (PSS+lysozyme) conformation modifies which is evidenced from the shifting of the amide-I band of each protein. However, irrespective of the conformation variation of proteins larger red-shifts of ≈30 nm in optical emissions are obtained from the thin films of PPC. Relatively enhance dissipation of energy thorough non-radiative transition of the fluorophore residues in the dry state is the most probable reason for such larger optical red-shifts.

  14. Architectures for block Toeplitz systems

    NARCIS (Netherlands)

    Bouras, Ilias; Glentis, George-Othon; Kalouptsidis, Nicholas

    1996-01-01

    In this paper efficient VLSI architectures of highly concurrent algorithms for the solution of block linear systems with Toeplitz or near-to-Toeplitz entries are presented. The main features of the proposed scheme are the use of scalar only operations, multiplications/divisions and additions, and th

  15. Tunable swelling of polyelectrolyte multilayers in cell culture media for modulating NIH-3T3 cells adhesion.

    Science.gov (United States)

    Qi, Wei; Cai, Peng; Yuan, Wenjing; Wang, Hua

    2014-11-01

    For polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer (LbL) assembly technique, their nanostructure and properties can be governed by many parameters during the building process. Here, it was demonstrated that the swelling of the PEMs containing poly(diallyldimethylammonium chloride) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS) in cell culture media could be tuned with changing supporting salt solutions during the assembly process. Importantly, the influence of the PEMs assembled in different salt solutions on NIH-3T3 cell adhesion was observable. Specifically, the cells could possess a higher affinity for the films assembled in low salt concentration (i.e. 0.15M NaCl) or no salt, the poorly swelling films in cell culture media, which was manifested by the large cell spreading area and focal adhesions. In contrast, those were assembled in higher salt concentration, highly swelling films in cell culture media, were less attractive for the fibroblasts. As a result, the cell adhesion behaviors may be manipulated by tailoring the physicochemical properties of the films, which could be performed by changing the assembly conditions such as supporting salt concentration. Such a finding might promise a great potential in designing desired biomaterials for tissue engineering and regenerative medicine.

  16. The influence of ionic strength and mixing ratio on the colloidal stability of PDAC/PSS polyelectrolyte complexes.

    Science.gov (United States)

    Zhang, Yanpu; Yildirim, Erol; Antila, Hanne S; Valenzuela, Luis D; Sammalkorpi, Maria; Lutkenhaus, Jodie L

    2015-10-01

    Polyelectrolyte complexes (PECs) form by mixing polycation and polyanion solutions together, and have been explored for a variety of applications. One challenge for PEC processing and application is that under certain conditions the as-formed PECs aggregate and precipitate out of suspension over the course of minutes to days. This aggregation is governed by several factors such as electrostatic repulsion, van der Waals attractions, and hydrophobic interactions. In this work, we explore the boundary between colloidally stable and unstable complexes as it is influenced by polycation/polyanion mixing ratio and ionic strength. The polymers examined are poly(diallyldimethylammonium chloride) (PDAC) and poly(sodium 4-styrenesulfonate) (PSS). Physical properties such as turbidity, hydrodynamic size, and zeta potential are investigated upon complex formation. We also perform detailed molecular dynamics simulations to examine the structure and effective charge distribution of the PECs at varying mixing ratios and salt concentrations to support the experimental findings. The results suggest that the colloidally stable/unstable boundary possibly marks the screening effects from added salt, resulting in weakly charged complexes that aggregate. At higher salt concentrations, the complexes initially form and then gradually dissolve into solution.

  17. PREPARATION OF POLYELECTROLYTE MULTILAYER COATED MICROBUBBLES FOR USE AS ULTRASOUND CONTRAST AGENT

    Institute of Scientific and Technical Information of China (English)

    Zhan-wen Xing; Heng-te Ke; Shao-qin Liu; Zhi-fei Dai; Jin-rui Wang; Ji-bin Liu

    2008-01-01

    Objective To prepare and characterize polyelectrolyte multilayer film coated microbubbles for use as ultrasound contrast agent (UCA) and evaluate its effects in ultrasonic imaging on normal rabbit's fiver parenchyma.Methoda Pcrfluorocarbon (PFC)-containing microbubbles (ST68-PFC) were prepared by sonication based on surfactant ( Span 60 and Tween 80). Subsequently, the resulting ST68-PFC microbnbbles were coated using oppositely charged polyclectrolytes by microbubble-templated layer-by-layer self-assembly technique via electrostatic interaction.The enhancement effects in ultrasonic imaging on normal rabbit's liver parenchyma were assessed.Results The obtained microbubbles exhibited a narrow size distribution. The polyelectrolytes were successfully assembled onto the surface of ST68-PFC microbubbles. In vivo experiment showed that polyelectrolyte multilayer film coated UCA effectively enhanced the imaging of rabbit's liver parenchyma.Conclnsions The novel microbubbles UCA coated with polyelectrolyte multilayer, when enabled more function,has no obvious difference in enhancement effects compared with the pre-modified microbnbbles. The polymers with chemically active groups ( such as amino group and carboxyl group) can be used as the outermost layer for attachment of targeting ligands onto microbubbles, allowing selective targeting of the microbubbles to combine with desired sites.

  18. Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

    NARCIS (Netherlands)

    Zielinska, K.; Leeuwen, van H.P.

    2014-01-01

    In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of

  19. A modified box model including charge regulation for protein adsorption in a spherical polyelectrolyte brush

    NARCIS (Netherlands)

    Biesheuvel, P.M.; Wittemann, A.

    2005-01-01

    Recent experiments showed significant adsorption of bovine serum albumin (BSA) in spherical polyelectrolyte brushes (SPB) consisting of polyacrylic acid, even for pH values above the isoelectric point of the protein, when both protein and polyion are negatively charged. To describe these experimenta

  20. Interaction of a hydophobic weak polyelectrolyte star with an apolar surface

    NARCIS (Netherlands)

    Rudd, O.V.; Leermakers, F.A.M.; Birshtein, T.M.

    2014-01-01

    We consider star-like polymers with weak, that is, pH-dependent, hydrophobic polyelectrolyte arms. For low ionic strength conditions, a microphase-segregated quasimicellar structure is found, for which the star features a compact apolar core and a charged and swollen corona. This state is jump-like

  1. Incorporation of a Cationic Conjugated Polyelectrolyte CPE within an Aqueous Poly(vinyl alcohol) Sol

    DEFF Research Database (Denmark)

    Knaapila, Matti; Stewart, Beverly; Costa, Telma

    2016-01-01

    We report on a multiscale polymer-within-polymer structure of the cationic conjugated polyelectrolyte poly{[9,9-bis(6-N,N,N-trimethylammonium)hexyl]fluorene phenylene} (HTMAPFP) in aqueous poly(vinyl alcohol).(PVA) sol. Molecular dynamics simulations and small-angle neutron scattering (SANS) data...

  2. Mechanism of rate enhancement of wood fiber saccharification by cationic polyelectrolytes.

    Science.gov (United States)

    Mora, Sandeep; Lu, Jian; Banerjee, Sujit

    2011-09-01

    Cationic polyelectrolytes can increase the cellulase-induced hydrolysis rates of bleached wood fiber. We show that the polymer associates mainly with the amorphous region of fiber and acts principally on endoglucanase. Fiber/water partitioning of the enzyme follows a Langmuir isotherm for the untreated fiber but a Freundlich isotherm is obeyed for the polymer-treated fiber.

  3. Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

    NARCIS (Netherlands)

    Zielinska, K.; Leeuwen, van H.P.

    2014-01-01

    In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of poly(diallyldimet

  4. Role of pH gradients in the actuation of electro-responsive polyelectrolyte gels

    NARCIS (Netherlands)

    Glazer, P.J.; van Erp, M.; Embrechts, A.; Lemay, Serge Joseph Guy; Mendes, E.

    2012-01-01

    Polyelectrolyte gels are able to mimic artificial muscles, swelling, shrinking or bending in response to environmental stimuli. Mechanical response is also observed in the presence of an electric field, in which case electrical energy is directly converted into mechanical energy. Although several

  5. The photoluminescent lifetime of polyelectrolytes in thin films formed via layer by layer self-assembly.

    Science.gov (United States)

    Reilly, Roseanne S; Smyth, Ciarán A; Rakovich, Yury P; McCabe, Eithne M

    2009-03-04

    We present results on luminescence lifetime studies of thin multilayer films of polyelectrolyte molecules produced via layer by layer (LbL) electrostatic assembly. We found that, in contrast to common assumptions, LbL films show measurable photoluminescent lifetimes with an average value of 6 ns. Scanning fluorescence lifetime imaging microscopy studies combined with steady-state photoluminescence measurements imply that this lifetime may be due to aggregation of polyelectrolyte molecules during preparation of LbL films. This conclusion has been further confirmed by atomic force microscopy (AFM). AFM images clearly show the presence of 100-200 nm high aggregates on the surface of these films. This aggregation of polyelectrolyte molecules contributes significantly to the experimentally detected luminescence decays of any light-emitting samples attached to LbL film, especially in a single molecule detection regime. To demonstrate this effect we compare photoluminescence lifetime results for CdTe quantum dots deposited on the surface of LbL polyelectrolyte films.

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

    Science.gov (United States)

    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…

  7. Self-consistent-field calculations of proteinlike incorporations in polyelectrolyte complex micelles

    NARCIS (Netherlands)

    Lindhoud, S.; Cohen Stuart, M.A.; Norde, W.; Leermakers, F.A.M.

    2009-01-01

    Self-consistent field theory is applied to model the structure and stability of polyelectrolyte complex micelles with incorporated protein (molten globule) molecules in the core. The electrostatic interactions that drive the micelle formation are mimicked by nearest-neighbor interactions using

  8. COAGULANT – POLYELECTROLYTE SYSTEM FOR THE CONDITIONING DIGESTED AND SONICATED SEWAGE SLUDGE

    Directory of Open Access Journals (Sweden)

    Beata Bień

    2014-10-01

    Full Text Available The article presents the results of research on the impact of inorganic coagulants and polyelectrolytes and their common action on sonicated digested sludge. Sonication of sludge samples was carried out under static conditions for 60, 120 and 180 seconds. The ultrasonic wave of f = 20 kHz and two different amplitudes of A = 15.25 μm was used in tests. The coagulant PIX123 and the polyelectrolyte Zetag 8160 were used for conditioning. On the basis of CST test the doses of chemical reagents were chosen for conditioning. The results showed the effect of application of the PIX123 and Zetag 8160 and their combination on non-sonicated and sonicated sludge. The lowest CST was achieved for non-sonicated sludge while polyelectrolyte was applied. For sonicated sludge better results were achieved when PIX123 was used. The combination of coagulant and polyelectrolyte allowed to achieve COD reduction, but the best results were achieved for sludge prepared by PIX123. The application of Zetag8160 in this case was not satisfactory.

  9. Static and ultrafast optical properties of nanolayered composites. Gold nanoparticles embedded in polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Kiel, Mareike

    2012-08-16

    In the course of this thesis gold nanoparticle/polyelectrolyte multilayer structures were prepared, characterized, and investigated according to their static and ultrafast optical properties. Using the dip-coating or spin-coating layer-by-layer deposition method, gold-nanoparticle layers were embedded in a polyelectrolyte environment with high structural perfection. Typical structures exhibit four repetition units, each consisting of one gold-particle layer and ten double layers of polyelectrolyte (cationic+anionic polyelectrolyte). The structures were characterized by X-ray reflectivity measurements, which reveal Bragg peaks up to the seventh order, evidencing the high stratification of the particle layers. In the same measurements pronounced Kiessig fringes were observed, which indicate a low global roughness of the samples. Atomic force microscopy (AFM) images verified this low roughness, which results from the high smoothing capabilities of polyelectrolyte layers. This smoothing effect facilitates the fabrication of stratified nanoparticle/polyelectrolyte multilayer structures, which were nicely illustrated in a transmission electron microscopy image. The samples' optical properties were investigated by static spectroscopic measurements in the visible and UV range. The measurements revealed a frequency shift of the reflectance and of the plasmon absorption band, depending on the thickness of the polyelectrolyte layers that cover a nanoparticle layer. When the covering layer becomes thicker than the particle interaction range, the absorption spectrum becomes independent of the polymer thickness. However, the reflectance spectrum continues shifting to lower frequencies (even for large thicknesses). The range of plasmon interaction was determined to be in the order of the particle diameter for 10 nm, 20 nm, and 150 nm particles. The transient broadband complex dielectric function of a multilayer structure was determined experimentally by ultrafast pump

  10. Transport rectification in nanopores with outer membranes modified with surface charges and polyelectrolytes.

    Science.gov (United States)

    Tagliazucchi, Mario; Rabin, Yitzhak; Szleifer, Igal

    2013-10-22

    This work reports a comprehensive theoretical study of the transport-rectification properties of cylindrical nanopores with neutral inner walls and chemically modified outer membrane. The chemical species on the two outer sides of the membrane have charges of opposite sign and can be either surface-confined species (i.e., surface charges) or polyelectrolyte brushes. The advantage of this design over other types of rectifying nanopores is that it requires controlling the composition of the outer walls of the pore (which are easy to access) rather than the inner walls, thus simplifying the fabrication process. Ion-current rectification in nanopores with charged outer walls is ascribed to applied-potential-induced changes in the ionic concentration within the pore. The rectification efficiency is studied as a function of pore length, radius, surface charge and bulk electrolyte concentration. An analytical model is derived for the case of surface-confined charges that predicts the current-potential curves in very good agreement with the numerical calculations. Neutral nanopores with polyelectrolyte-modified outer walls have two distinct advantages compared to surface-charged systems: (i) they exhibit higher rectification factors due to the large charge density immobilized by the polyelectrolyte brushes, and (ii) the applied potential deforms the polyelectrolyte chains toward the oppositely charged electrode. This deformation brings the polyelectrolyte brushes into the pore in the low conductivity state and expels them from the pore in the high conductivity regime. Calculations of the potentials of mean-force suggest that the applied-field-induced conformational changes can be used to control the translocation of cargoes larger than ions, such as proteins and nanoparticles.

  11. Cytotoxicity and antibacterial property of titanium alloy coated with silver nanoparticle-containing polyelectrolyte multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xinming [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Li, Zhaoyang [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China); Yuan, Xubo [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Cui, Zhenduo [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China); Bao, Huijing; Li, Xue; Liu, Yunde [School of Laboratory Medicine, Tianjin Medical University, Tianjin, 300203 (China); Yang, Xianjin, E-mail: xjyang@tju.edu.cn [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China)

    2013-07-01

    Silver nanoparticle (AgNP) was incorporated into dopamine-modified alginate/chitosan (DAL/CHI) polyelectrolyte multilayer to modify the surface of titanium alloy and improve its antibacterial property. Scanning electron microscopy showed that AgNP with the size of 50 nm embedded in DAL/CHI multilayers homogeneously. X-ray photoelectron spectroscopy analysis indicated that the nanoparticles were silver (0) with peaks at 368.4 and 374.4 eV, respectively. The formation of silver (0) without the addition of reductants was due to the self-polymerization of dopamine, which can reduce the silver cation into neutral metal. The polyelectrolyte multilayer coating enhanced the wettability of titanium alloy and promoted the fibroblast proliferation significantly, which could be attributed to the excellent biocompatibility of DAL/CHI. Despite the slight fall of L929 cell activity after AgNP incorporation, AgNP-DAL/CHI multilayer inhibited the growth of both Escherichia coli and Staphylococcus aureus. The above results demonstrate that dopamine decoration is a simple and effective way to induce the in-situ formation of AgNP within polyelectrolyte multilayer. Furthermore, the AgNP-containing multilayer considerably enhances the antibacterial activity of titanium alloy. The fabrication of AgNP-DAL/CHI multilayer on the surface of titanium implant might have great potential in orthopedic use. - Highlights: • Polyelectrolyte multilayer was fabricated through layer-by-layer assembly. • AgNP was formed in-situ and embedded within polyelectrolyte multilayer. • Surface of titanium was modified by AgNP-DAL/CHI multilayer with a facile method. • AgNP-DAL/CHI multilayer enhanced antibacterial activity of titanium alloy.

  12. FORMULATION AND EVALUATION OF MATRIX TABLETS BASED ON POLYELECTROLYTE COMPLEX BETWEEN OKRA MUCILAGE AND CHITOSAN

    Directory of Open Access Journals (Sweden)

    Ashwini Rajendra

    2012-02-01

    Full Text Available Recent years there has been greater utilization of natural polymers in the development of delivery systems. The present work is an effort towards development of matrix tablets using polyelectrolyte complex formed between the oppositely charged natural polymers like okra mucilage obtained from pods of Abelmoschus esculentus and chitosan. The effect of pH and polymer volume ratio on yield of polyelectrolyte complex was studied. It was observed that the yield was maximum (96.45% at pH 5 and at polymer volume ratio of 9:1 between okra mucilage and chitosan. The prepared polyelectrolyte complex was also characterised by conductimetry, FTIR, DSC. The results confirmed the formation of polyelectrolyte complex between the natural polymers. The matrix tablets were formulated for model drug diclofenac sodium using the best polyelectrolyte complex at different drug to polymer ratios and compared with formulations containing individual polymers as well as marketed formulation. The prepared formulations showed satisfactory physical parameters. Formulations F2 and F3 extended the drug release for more than 8 h with (83.87± 0.8321% and (77.125± 0.125% drug release respectively in 8 h. The formulations F2 and F3 followed zero order kinetics with anomalous diffusion mechanism. The mean dissolution times were 3.6042 and 3.5935 hrs and the % dissolution efficiency were 54.9467 and 55.7203 % for formulations F2 and F3 respectively. The similarity factor f2 for formulation F2 was 61.6751 and for formulation F3, it was found to be 60.5025.The formulations were found to be stable.

  13. Ultrasound guided supraclavicular block.

    LENUS (Irish Health Repository)

    Hanumanthaiah, Deepak

    2013-09-01

    Ultrasound guided regional anaesthesia is becoming increasingly popular. The supraclavicular block has been transformed by ultrasound guidance into a potentially safe superficial block. We reviewed the techniques of performing supraclavicular block with special focus on ultrasound guidance.

  14. Phase behavior of electrostatically complexed polyelectrolyte gels using an embedded fluctuation model.

    Science.gov (United States)

    Audus, Debra J; Gopez, Jeffrey D; Krogstad, Daniel V; Lynd, Nathaniel A; Kramer, Edward J; Hawker, Craig J; Fredrickson, Glenn H

    2015-02-14

    Nanostructured, responsive hydrogels formed due to electrostatic interactions have promise for applications such as drug delivery and tissue mimics. These physically cross-linked hydrogels are composed of an aqueous solution of oppositely charged triblocks with charged end-blocks and neutral, hydrophilic mid-blocks. Due to their electrostatic interactions, the end-blocks microphase separate and form physical cross-links that are bridged by the mid-blocks. The structure of this system was determined using a new, efficient embedded fluctuation (EF) model in conjunction with self-consistent field theory. The calculations using the EF model were validated against unapproximated field-theoretic simulations with complex Langevin sampling and were found consistent with small angle X-ray scattering (SAXS) measurements on an experimental system. Using both the EF model and SAXS, phase diagrams were generated as a function of end-block fraction and polymer concentration. Several structures were observed including a body-centered cubic sphere phase, a hexagonally packed cylinder phase, and a lamellar phase. Finally, the EF model was used to explore how parameters that directly relate to polymer chemistry can be tuned to modify the resulting phase diagram, which is of practical interest for the development of new hydrogels.

  15. Effect of thiocyanate counterion condensation on poly(allylamine hydrochloride) chains on the buildup and permeability of polystyrenesulfonate/polyallylamine polyelectrolyte multilayers.

    Science.gov (United States)

    Ball, Vincent; Voegel, Jean-Claude; Schaaf, Pierre

    2005-04-26

    In this study, we investigate the buildup of PEI-(PSS-PAH)(n) polyelectrolyte multilayers at pH 7.4 in the presence of either NaCl or NaSCN as a supporting electrolyte. It appears that in the presence of increasing thiocyanate concentrations (from 0.1 to 0.5 M), the thickness increment, obtained from optical waveguide lightmode spectroscopy experiments, increases whereas it stays practically constant for increasing sodium chloride concentrations (between 0.1 and 0.5 M). The hydration of the films differs also markedly between both electrolyte solutions. The differences in the construction of the polyelectrolyte multilayers in the presence of both supporting electrolytes are rationalized in terms of strong SCN(-) condensation on the PAH chains. The occurrence of this ion condensation is indirectly demonstrated by means of zeta potential measurements and directly demonstrated by means of attenuated total internal reflection infrared spectroscopy on the multilayer films. Moreover when the films are built up in the presence of SCN(-), these ions are only slowly exchanged by the Cl(-) ions introduced in the bulk. Conversely the thick films obtained from 0.5 M NaSCN solutions do not deswell when the buffer solution is replaced by a 0.5 M NaCl containing buffer. The permeability of the films constructed in the presence of both sodium salts is also studied by means of cyclic voltametry and is found to be markedly different in the case of films made from five bilayers at 0.5 M salt concentration. This difference is due to the different morphology and porosity of the films constructed in the presence of 0.5 M NaCl and 0.5 M NaSCN.

  16. NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    Guojun Liu

    2000-01-01

    Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, selfassembly, selective domain crosslinking, and sometimes selective domain removal. Preparation of thin films with nanochannels was used to illustrate the strategy we took. In this particular case, a linear triblock copolymer polyisopreneblock-poly(2-cinnamoylethyl methacrylate)-block-poly(t-butyl acrylate), PI-b-PCEMA-b-PtBA, was used. Films, 25 to50μm thick, were prepared from casting on glass slides a toluene solution of PI-b-PCEMA-b-PtBA and PtBA homopolymer,hPtBA, where hPtBA is shorter than the PtBA block. At the hPtBA mass fraction of 20% relative to the triblock or the total PtBA (hPtBA and PtBA block) volume fraction of 0.44, hPtBA and PtBA formed a seemingly continuous phase in the matrix of PCEMA and PI. Such a block segregation pattern was locked in by photocrosslinking the PCEMA domain. Nanochannels were formed by extracting out hPtBA with solvent. Alternatively, larger channels were obtained from extracting out hPtBA and hydrolyzing the t-butyl groups of the PtBA block. Such membranes were not liquid permeable but had gas permeability constants ~6 orders of magnitude higher than that of low-density polyethylene films.

  17. Layer-by-layer self-assembly of composite polyelectrolyte-Nafion membranes for direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, S.P.; Liu, Z.; Tian, Z.Q. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

    2006-04-18

    A novel composite polyelectrolyte/Nafion membrane is demonstrated that is fabricated using the layer-by-layer self-assembly of oppositely charged polyelectrolytes. A direct methanol fuel cell based on such a membrane is shown to achieve a significant reduction in methanol crossover and an increase in power density of 42 %, in comparison to that which uses a pristine Nafion membrane. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

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

    OpenAIRE

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

    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...

  19. Dissipative particle dynamics simulations of weak polyelectrolyte adsorption on charged and neutral surfaces as a function of the degree of ionization

    CERN Document Server

    Alarcón, F; Goicochea, A Gama

    2012-01-01

    The influence of the chain degree of ionization on the adsorption of weak polyelectrolytes on neutral and on oppositely and likely charged surfaces is investigated for the first time, by means of Monte Carlo simulations with the mesoscopic interaction model known as dissipative particle dynamics. The electrostatic interactions are calculated using the three-dimensional Ewald sum method, with an appropriate modification for confined systems. Effective wall forces confine the linear polyelectrolytes, and electric charges on the surfaces are included. The solvent is included explicitly also and it is modeled as an athermal solvent for the polyelectrolytes. The number of solvent particles is allowed to fluctuate. The results show that the polyelectrolytes adsorb both onto neutral and charged surfaces, with the adsorption regulated by the chain degree of ionization, being larger at lower ionization degrees, where polyelectrolytes are less charged. Furthermore, polyelectrolyte adsorption is strongly modulated by th...

  20. Biocompatible long-sustained release oil-core polyelectrolyte nanocarriers: From controlling physical state and stability to biological impact.

    Science.gov (United States)

    Szczepanowicz, Krzysztof; Bazylińska, Urszula; Pietkiewicz, Jadwiga; Szyk-Warszyńska, Lilianna; Wilk, Kazimiera A; Warszyński, Piotr

    2015-08-01

    It has been generally expected that the most applicable drug delivery system (DDS) should be biodegradable, biocompatible and with incidental adverse effects. Among many micellar aggregates and their mediated polymeric systems, polyelectrolyte oil-core nanocarriers have been found to successfully encapsulate hydrophobic drugs in order to target cells and avoid drug degradation and toxicity as well as to improve drug efficacy, its stability, and better intracellular penetration. This paper reviews recent developments in the formation of polyelectrolyte oil-core nanocarriers by subsequent multilayer adsorption at micellar structures, their imaging, physical state and stability, drug encapsulation and applications, in vitro release profiles and in vitro biological evaluation (cellular uptake and internalization, biocompatibility). We summarize the recent results concerning polyelectrolyte/surfactant interactions at interfaces, fundamental to understand the mechanisms of formation of stable polyelectrolyte layered structures on liquid cores. The fabrication of emulsion droplets stabilized by synergetic surfactant/polyelectrolyte complexes, properties, and potential applications of each type of polyelectrolyte oil-core nanocarriers, including stealth nanocapsules with pegylated shell, are discussed and evaluated. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Layer-by-layer self-assembly of polyelectrolyte functionalized MoS2 nanosheets

    Science.gov (United States)

    Shen, Jianfeng; Pei, Yu; Dong, Pei; Ji, Jin; Cui, Zheng; Yuan, Junhua; Baines, Robert; Ajayan, Pulickel M.; Ye, Mingxin

    2016-05-01

    Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems.Few-layered polyelectrolyte functionalized MoS2 nanosheets were obtained for the first time through in situ polymerization of MoS2 nanosheets with poly(acrylic acid) and poly(acrylamide), both of which demonstrated excellent dispersibility and stability in water. After designing and optimizing the components of this series of polyelectrolyte functionalized MoS2 nanosheets, by exploiting the electrostatic interactions present in the modified MoS2 nanosheets, we further created a series of layer-by-layer (LBL) self-assembling MoS2-based films. To this end, uniform MoS2 nanosheet-based LBL films were precisely deposited on substrates such as quartz, silicon, and ITO. The polyelectrolyte functionalized MoS2 nanosheet assembled LBL film-modified electrodes demonstrated enhanced electrocatalytic activity for H2O2. As such, they are conducive to efficient sensors and advanced biosensing systems. Electronic supplementary information (ESI) available: SEM, AFM and TEM characterization of PAA-MoS2 and PAM-MoS2 nanocomposites. More characterization and electrochemical properties of LBL films

  2. Block-based image hashing with restricted blocking strategy for rotational robustness

    Science.gov (United States)

    Xiang, Shijun; Yang, Jianquan

    2012-12-01

    Image hashing is a potential solution for image content authentication (a desired image hashing algorithm should be robust to common image processing operations and various geometric distortions). In the literature, researchers pay more attention to block-based image hashing algorithms due to their robustness to common image processing operations (such as lossy compression, low-pass filtering, and additive noise). However, the block-based hashing strategies are sensitive to rotation processing operations. This indicates that the robustness of the block-based hashing methods against rotation operations is an important issue. Towards this direction, in this article we propose a restricted blocking strategy by investigating effect of two rotation operations on an image and its blocks in both theoretical and experimental ways. Furthermore, we apply the proposed blocking strategy for the recently reported non-negative matrix factorization (NMF) hashing. Experimental results have demonstrated the validity of the block-based hashing algorithms with restricted blocking strategy for rotation operations.

  3. Preparation of polyelectrolyte complex nanoparticles of chitosan and poly(2-acry1amido-2-methylpropanesulfonic acid) for doxorubicin release.

    Science.gov (United States)

    Zhang, Liping; Wang, Jie; Ni, Caihua; Zhang, Yanan; Shi, Gang

    2016-01-01

    A new kind of polyelectrolyte complex (PEC) based on cationic chitosan (CS) and anionic poly(2-acry1amido-2-methylpropanesulfonic acid) (PAMPS) was prepared using a polymer-monomer pair reaction system. Chitosan was mixed with 2-acry1amido-2-methylpropanesulfonic acid) (AMPS) in an aqueous solution, followed by polymerization of AMPS. The complex was formed by electrostatic interaction of NH3(+) groups of CS and SO3(-) groups of AMPS, leading to a formation of complex nanoparticles of CS-PAMPS. A series of nanoparticles were obtained by changing the weight ratio of CS to AMPS, the structure and properties of nanoparticles were investigated. It was observed that the nanoparticles possessed spherical morphologies with average diameters from 255 nm to 390 nm varied with compositions of the nanoparticles. The nanoparticles were used as drug vehicles for doxorubicin, displaying relative high drug loading rate and encapsulation rate. The vitro release profiles revealed that the drug release could be controlled by adjusting pH of the release media. The nanoparticles demonstrated apparent advantages such as simple preparation process, free of organic solvents, size controllable, good biodegradability and biocompatibility, and they could be potentially used in drug controlled release field.

  4. Polyelectrolyte Conformation, Interactions and Hydrodynamics as Studied by Light Scattering.

    Science.gov (United States)

    Ghosh, Snehasish

    Polyelectrolyte conformation, interactions and hydrodynamics show a marked dependence on the ionic strength (C_{rm s}) of the medium, the concentration (C_{rm p}) of the polymer itself and their charge density (xi). The apparent electrostatic persistence length obtained from static light scattering varied approximately as the inverse square root of C _{rm s} for highly pure, high molecular weight hyaluronate (HA) as well as for variably ionized acrylamide/sodium acrylate copolymers (NaPAA), and linearly with xi. The experimental values of persistence length and second virial coefficient (A_2) are compared to predictions from theories based on the Debye-Huckel approximation for the Poisson-Boltzmann equation and on excluded-volume. Although the mean square radius of gyration () depended strongly on C _{rm s}. decreasing with increasing C_{rm s} for both HA and NaPAA indicating clear evidence of polyion expansion, dynamic light scattering values of the translational diffusion coefficient (D) remains constant when extrapolated to infinite polymer concentration for both the polymers. The behavior of D is compared to predictions from coupled mode theory in the linear limit. The effects of NaOH on the conformations, interactions, diffusion and hydrolysis rates of HA are characterized in detail using static, dynamic and time-dependent light scattering supplemented by size exclusion chromatography (SEC). For the HA , A_2 and the hydrolysis rates all resemble superposing titration curves, while the D remains independent of both the concentration of NaOH, and the contraction of . The indication is that the interactions, conformations and the hydrolysis rates are all controlled by the titration of the HA hydroxyl groups by the NaOH to yield -O ^-, which (i) destroys single strand hydrogen bonds, leading to de-stiffening and contraction of the HA coil and a large decrease in intermolecular interaction, and (ii) slowly depolymerizes HA. The experimental results of HA

  5. Direct surface force measurements of polyelectrolyte multilayer films containing nanocrystalline cellulose.

    Science.gov (United States)

    Cranston, Emily D; Gray, Derek G; Rutland, Mark W

    2010-11-16

    Polyelectrolyte multilayer films containing nanocrystalline cellulose (NCC) and poly(allylamine hydrochloride) (PAH) make up a new class of nanostructured composite with applications ranging from coatings to biomedical devices. Moreover, these materials are amenable to surface force studies using colloid-probe atomic force microscopy (CP-AFM). For electrostatically assembled films with either NCC or PAH as the outermost layer, surface morphology was investigated by AFM and wettability was examined by contact angle measurements. By varying the surrounding ionic strength and pH, the relative contributions from electrostatic, van der Waals, steric, and polymer bridging interactions were evaluated. The ionic cross-linking in these films rendered them stable under all solution conditions studied although swelling at low pH and high ionic strength was inferred. The underlying polymer layer in the multilayered film was found to dictate the dominant surface forces when polymer migration and chain extension were facilitated. The precontact normal forces between a silica probe and an NCC-capped multilayer film were monotonically repulsive at pH values where the material surfaces were similarly and fully charged. In contrast, at pH 3.5, the anionic surfaces were weakly charged but the underlying layer of cationic PAH was fully charged and attractive forces dominated due to polymer bridging from extended PAH chains. The interaction with an anionic carboxylic acid probe showed similar behavior to the silica probe; however, for a cationic amine probe with an anionic NCC-capped film, electrostatic double-layer attraction at low pH, and electrostatic double-layer repulsion at high pH, were observed. Finally, the effect of the capping layer was studied with an anionic probe, which indicated that NCC-capped films exhibited purely repulsive forces which were larger in magnitude than the combination of electrostatic double-layer attraction and steric repulsion, measured for PAH

  6. Interferometry study of aqueous lubrication on the surface of polyelectrolyte brush.

    Science.gov (United States)

    Kobayashi, Motoyasu; Tanaka, Hiroyoshi; Minn, Myo; Sugimura, Joichi; Takahara, Atsushi

    2014-11-26

    The water lubrication behavior of a polyelectrolyte brush was investigated by using double-spacer-layer ultra-thin-film interferometry to determine the thickness of the aqueous lubrication layer present at the interface between the brush and a spherical glass lens. A hydrophilic poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride} brush was prepared on an optical glass disk coated with layers of semireflective chromium and silica. The thickness of the hydrodynamic lubrication layer was estimated interferometrically. On increasing the sliding velocity from 10(-5) to 10(-1) m·s(-1), the gap between the rotating disk and loading sphere glass lens showed a marked increase to 130 nm at 2×10(-2) m·s(-1), and the friction coefficient simultaneously decreased to 0.01-0.02, indicating that the polyelectrolyte brush promoted the formation of a fluid lubrication layer that separates the rubbing surfaces, preventing direct contact and providing a low friction coefficient.

  7. Low Molecular Weight Chitosan–Insulin Polyelectrolyte Complex: Characterization and Stability Studies

    Directory of Open Access Journals (Sweden)

    Zakieh I. Al-Kurdi

    2015-03-01

    Full Text Available The aim of the work reported herein was to investigate the effect of various low molecular weight chitosans (LMWCs on the stability of insulin using USP HPLC methods. Insulin was found to be stable in a polyelectrolyte complex (PEC consisting of insulin and LMWC in the presence of a Tris-buffer at pH 6.5. In the presence of LMWC, the stability of insulin increased with decreasing molecular weight of LMWC; 13 kDa LMWC was the most efficient molecular weight for enhancing the physical and chemical stability of insulin. Solubilization of insulin-LMWC polyelectrolyte complex (I-LMWC PEC in a reverse micelle (RM system, administered to diabetic rats, results in an oral delivery system for insulin with acceptable bioactivity.

  8. Stable Aqueous Suspension and Self-Assembly of Graphite Nanoplatelets Coated with Various Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Jue Lu

    2010-01-01

    Full Text Available Exfoliated graphite nanoplatelets (xGnPs with an average thickness of 1–10 nm present an inexpensive alternative to carbon nanotubes in many applications. In this paper, stable aqueous suspension of xGnP was achieved by noncovalent functionalization of xGnP with polyelectrolytes. The surfactants and polyelectrolytes were compared with respect to their ability to suspend graphite nanoplatelets. The surface charge of the nanoplatelets was characterized with zeta potential measurements, and the bonding strength of the polymer chains to the surface of xGnP was characterized with Raman spectroscopy. This robust method opens up the possibility of using this inexpensive nanomaterial in many applications, including electrochemical devices, and leads to simple processing techniques such as layer-by-layer deposition. Therefore, the formation of xGnP conductive coatings using layer-by-layer deposition was also demonstrated.

  9. Interest of Polyelectrolyte Multilayer thin Films in Tissue Engineering:Application to Vascular Allograft

    Institute of Scientific and Technical Information of China (English)

    Halima KERDJOUDJ; Cedric BOURA; Vanessa MOBY; Dominique DUMAS; Luc MARCHAL; Jean-Claude VOEGEL; Jean-Fran(c)ois STOLTZ; Patrick MENU

    2005-01-01

    @@ 1 Introduction Obstructive atherosclerosis vascular disease remains one of the greatest public health threats in the world. Surgical treatment to replace diseased blood vessels is usually done using major human allografts (veins or arteries) or synthetic prosthesis ( PTFE, Dacron). However, these substitutes have not a good pateney, because of the lack of endothelial cells (ECs) layer, which prevents thrombus formation. The challenge of tissue engineering vessels is to build-up blood/substitute interface near native vessels.In order to improve ECs adhesion, it is necessary to precoat the intra-luminal vessel. Recently, a new surface modification technique arose, based on the alternate adsorption of oppositely charged polyelectrolytes. Our objective was to favour the endothelialization of the cryo-preserved allografts, treated with a thin polyelectrolyte multilayered film, made of PSS (poly (sodium-4-styrenesulfonate) ) or PAH (poly (allylamine hydrochloride) ).

  10. Cell adhesive behavior on thin polyelectrolyte multilayers: cells attempt to achieve homeostasis of its adhesion energy.

    Science.gov (United States)

    Mehrotra, Sumit; Hunley, S Christopher; Pawelec, Kendell M; Zhang, Linxia; Lee, Ilsoon; Baek, Seungik; Chan, Christina

    2010-08-03

    Linearly growing ultrathin polyelectrolyte multilayer (PEM) films of strong polyelectrolytes, poly(diallyldimethylammonium chloride) (PDAC), and sulfonated polystyrene, sodium salt (SPS) exhibit a gradual shift from cytophilic to cytophobic behavior, with increasing thickness for films of less than 100 nm. Previous explanations based on film hydration, swelling, and changes in the elastic modulus cannot account for the cytophobicity observed with these thin films as the number of bilayers increases. We implemented a finite element analysis to help elucidate the observed trends in cell spreading. The simulation results suggest that cells maintain a constant level of energy consumption (energy homeostasis) during active probing and thus respond to changes in the film stiffness as the film thickness increases by adjusting their morphology and the number of focal adhesions recruited and thereby their attachment to a substrate.

  11. Counterions release from electrostatic complexes of polyelectrolytes and proteins of opposite charge : a direct measurement

    CERN Document Server

    Gummel, Jérémie; Boué, François

    2009-01-01

    Though often considered as one of the main driving process of the complexation of species of opposite charges, the release of counterions has never been experimentally directly measured on polyelectrolyte/proteins complexes. We present here the first structural determination of such a release by Small Angle Neutron Scattering in complexes made of lysozyme, a positively charged protein and of PSS, a negatively charged polyelectrolyte. Both components have the same neutron density length, so their scattering can be switched off simultaneously in an appropriate "matching" solvent; this enables determination of the spatial distribution of the single counterions within the complexes. The counterions (including the one subjected to Manning condensation) are expelled from the cores where the species are at electrostatic stoichiometry.

  12. Suitability of polyelectrolyte shells modified with fullerene derivate for immunoisolation of cells. Experimental study.

    Science.gov (United States)

    Borkowska, M; Godlewska, E; Antosiak-Iwańska, M; Kinasiewicz, J; Strawski, M; Szklarczyk, M; Granicka, L H

    2012-12-01

    The polymeric permiselective membranes application for immunoisolation of cells separating the transplanted cells from the host immunological system may eliminate immunosuppressive therapy during transplantation. The suitability of polyelectrolyte modified nanocoatings for immunoisolation of cells was assessed. The polymeric shells modified with incorporated fullerene derivate were applied for encapsulation of human T-lymphocyte cell line Jurkat or rat pancreatic islets of Langerhans using layer-by-layer technique. Hydroxylated fullerene was incorporated to the polyelectrolyte shell for hydrophility increase as well as for layer stability improvement. Evaluation with AFM, FTIR, fluorescence microscopy confirmed the nanocoating presence on the encapsulated cells. It was observed that polylysine-polyethyleneimine membrane with incorporated fullerenol allowed for encapsulated cells functioning in vitro. Membrane conformation applied for encapsulation of pancreatic rat islets allowed for glucose level decline during xenotransplantation into mice. The elaborated nanocoating may be recommended as the possible alternative to the space consuming microencapsulation for biomedical purposes.

  13. Spherical polyelectrolyte brushes as a nanoreactor for synthesis of ultrafine magnetic nanoparticles

    Science.gov (United States)

    Zhu, Yan; Chen, Kaimin; Wang, Xiang; Guo, Xuhong

    2012-07-01

    Ultrafine magnetic nanoparticles (MNP, 1.4-5.8 nm) were generated within a nanoreactor of spherical polyelectrolyte brushes (SPB). SPB consist of a solid polystyrene (PS) core and densely grafted poly(acrylic acid) (PAA) chains. Due to strong chemical coordination between carboxyl groups in PAA and MNP surfaces, the obtained magnetic spherical polyelectrolyte brushes (MSPB) kept excellent stability and maintained pH sensitivity. The magnetic properties of MSPB were confirmed by a vibrating sample magnetometer (VSM). The size and the size dispersion of MNP can be modulated by varying adding sequences (conventional coprecipitation or reverse coprecipitation), or nanoreactor structure (with or without crosslinking). MNP content in MSPB could be adjusted by multicycle reactions. This new strategy makes it possible to synthesize ultrafine inorganic nanoparticles with tunable size in SPB.

  14. Langmuir and langmuir-blodgett films of metallosupramolecular polyelectrolyte-amphiphile complexes.

    Science.gov (United States)

    Lehmann, Pit; Symietz, Christian; Brezesinski, Gerald; Krass, Henning; Kurth, Dirk G

    2005-06-21

    A detailed analysis of a metallosupramolecular polyelectrolyte-amphiphile complex (PAC) at the air-water interface is presented. Langmuir isotherms, Brewster angle microscopy, and X-ray reflectance and diffraction methods are employed to investigate the structure of the Langmuir monolayers. The PAC is self-assembled from 1,3-bis[4'-oxa-(2,2':6',2' '-terpyridinyl)]propane, iron acetate, and dihexadecyl phosphate (DHP). Spreading the PAC at the air-water interface results in a monolayer that consists of two strata. DHP forms a monolayer at the top of the interface, while the metallosupramolecular polyelectrolyte is immersed in the aqueous subphase. Both strata are coupled to each other through electrostatic interactions. The monolayers can be transferred onto solid substrates, resulting in well-ordered multilayers. Such multilayers are model systems for well-ordered metal ions in two dimensions.

  15. Ultrasonic compatibilization of polyelectrolyte complex based on polysaccharides for biomedical applications

    OpenAIRE

    Belluzo, M. Soledad; Medina, Lara F.; Cortizo, Ana María; Cortizo, María Susana

    2016-01-01

    In recent years, there has been an increasing interest in the design of biomaterials for cartilage tissue engineering. This type of materials must meet several requirements. In this study, we apply ultrasound to prepare a compatibilized blend of polyelectrolyte complexes (PEC) based on carboxymethyl cellulose (CMC) and chitosan (CHI), in order to improve stability and mechanical properties through the interpolymer macroradicals coupling produced by sonochemical reaction. We study the kinetic ...

  16. Charge regulation of weak polyelectrolytes at low- and high-dielectric-constant substrates

    CERN Document Server

    Netz, R R

    2003-01-01

    As is well known, the effective charge of weak polyelectrolytes (PEs) decreases with decreasing salt concentration due to the electrostatic repulsion between dissociated charges. Close to dielectric boundaries, image-charge effects influence the dissociation equilibrium. At low-dielectric-constant substrates, one finds a further charge decrease and repulsion from the interface, while at high-dielectric-constant (e.g. metallic) substrates, the effective charge increases and the PE is attracted to the interface.

  17. Biomimetic hydration lubrication with various polyelectrolyte layers on cross-linked polyethylene orthopedic bearing materials.

    Science.gov (United States)

    Kyomoto, Masayuki; Moro, Toru; Saiga, Kenichi; Hashimoto, Masami; Ito, Hideya; Kawaguchi, Hiroshi; Takatori, Yoshio; Ishihara, Kazuhiko

    2012-06-01

    Natural joints rely on fluid thin-film lubrication by the hydrated polyelectrolyte layer of cartilage. However, current artificial joints with polyethylene (PE) surfaces have considerably less efficient lubrication and thus much greater wear, leading to osteolysis and aseptic loosening. This is considered a common factor limiting prosthetic longevity in total hip arthroplasty (THA). However, such wear could be mitigated by surface modification to mimic the role of cartilage. Here we report the development of nanometer-scale hydrophilic layers with varying charge (nonionic, cationic, anionic, or zwitterionic) on cross-linked PE (CLPE) surfaces, which could fully mimic the hydrophilicity and lubricity of the natural joint surface. We present evidence to support two lubrication mechanisms: the primary mechanism is due to the high level of hydration in the grafted layer, where water molecules act as very efficient lubricants; and the secondary mechanism is repulsion of protein molecules and positively charged inorganic ions by the grafted polyelectrolyte layer. Thus, such nanometer-scaled hydrophilic polymers or polyelectrolyte layers on the CLPE surface of acetabular cup bearings could confer high durability to THA prosthetics.

  18. Densely charged polyelectrolyte-stuffed nanochannel arrays for power generation from salinity gradient

    Science.gov (United States)

    Kwak, Su Hong; Kwon, Seung-Ryong; Baek, Seol; Lim, Seung-Min; Joo, Young-Chang; Chung, Taek Dong

    2016-05-01

    We devised anodized aluminium oxide (AAO) frame-supported polyelectrolytic ion-exchange membranes for the application of electrical power generation systems where salinity differences are present. A series of polyelectrolytic AAO membranes (PAMs) were fabricated as a function of concentration of monomers and cross-linkers. Of the ion-selective PAMs as made, the membranes from the most concentrated monomers and cross-linkers, C-PAM100 and A-PAM100, showed the highest area resistances and permselectivities (the resistances were 4.9 and 2.9 Ω · cm2, the permseletivities for C-PAM100 and A-PAM100 were 99 and 89%, respectively). The measured resistances and permselectivities allowed the power density to be estimated for C-PAM100 and A-PAM100, 3.5 W/m2, and experimentally obtained power density using a reverse electrodialysis (RED) stack was 17.3 mW/m2. In addition, we investigated the influence of an AAO framework on a membrane resistance by comparing the PAMs with polyelectrolyte-stuffed capillaries, revealing that the resistance of the PAM has plenty of potential to be further reduced by optimizing the AAO pore spaces.

  19. Liquid-liquid and liquid-solid phase separation in protein-polyelectrolyte systems.

    Science.gov (United States)

    Comert, Fatih; Dubin, Paul L

    2017-01-01

    The coacervation of systems containing colloids (e.g. proteins or micelles) and polyelectrolytes (notably ionic polysaccharides) is often accompanied by precipitation. This can introduce inhomogeneity, irreversibility and irreproducible kinetics in applications in food science and bioengineering, with negative impact on texture and stability of food products, and unpredictable delivery of active "payloads." The relationship between coacervation and precipitation is obscure in that coacervates might be intermediates in the formation of precipitates, or else the two phenomena might proceed by different but possibly simultaneous mechanisms. This review will summarize the recent literature on coacervation/precipitation in protein-polyelectrolyte systems for which reports are most abundant, particularly in the context of food science. We present current findings and opinions about the relationship between the two types of phase separation. Results vary considerably depending not only on the protein-polyelectrolyte pairs chosen, but also on conditions including macromolecular concentrations and ionic strength. Nevertheless, we offer some general approaches that could explain a variety of observations. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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

  1. Molecular-dynamics simulations and x-ray analysis of dye precipitates in the polyelectrolyte microcapsules

    Science.gov (United States)

    Saphiannikova, Marina; Radtchenko, Igor; Sukhorukov, Gleb; Shchukin, Dmitri; Yakimansky, Alexander; Ilnytskyi, Jaroslav

    2003-05-01

    The precipitate of the Disperse Red-1 dye in bulk and in confined microsized volumes was investigated by x-ray powder diffraction and molecular-dynamics simulations. The diffraction patterns exhibited two different precipitation regimes: In bulk when dye molecules form a distinct crystallite structure and inside polyelectrolyte capsules with a diameter up to 8 μm when the precipitate presumably represents a very fine polycrystalline powder. The latter result was further supported by molecular-dynamics simulations carried out for up to 640 dye molecules in the NVT ensemble. Calculations have also shown that effects of confined geometry and steric restrictions arising due to encapsulated polyelectrolyte molecules can not prohibit dye nucleation and subsequent crystallization. However, nonspecific interactions between Disperse Red-1 and encapsulated polyelectrolyte could cause the onset of heterogeneous nucleation resulting in formation of a fine polycrystalline powder. The formation process was directly observed building configuration snapshots and calculating the Gay-Berne orientational order parameter and radial distribution function resolved parallel and perpendicular to the director. Comparison of powder diagrams derived from simulation data indicates that it is nearly impossible to distinguish a fine polycrystalline powder from the isotropic system.

  2. Filterability of membrane bioreactor (MBR) sludge: impacts of polyelectrolytes and mixing with conventional activated sludge.

    Science.gov (United States)

    Yigit, Nevzat O; Civelekoglu, Gokhan; Cinar, Ozer; Kitis, Mehmet

    2010-01-01

    The main objective of this work was to investigate the filterability of MBR sludge and its mixture with conventional activated sludge (CAS). In addition, the impacts of type and dose of various polyelectrolytes, filter type and sludge properties on the filterability of both MBR and Mixed sludges were determined. Specific cake resistance (SCR) measured by the Buchner funnel filtration test apparatus and the solids content of the resulting sludge cake were used to assess the dewaterability of tested sludges. The type of filter paper used in Buchner tests affected the results of filterability for MBR, CAS and Mixed sludges. SCR values and optimum polyelectrolyte doses increased with increasing MLSS concentrations in the MBR, which suggested that increase in MLSS concentrations accompanied by increases in EPS and SMP concentrations and a shift toward smaller particles caused poorer dewaterability of the MBR sludge. The significant differences observed among the filterability of CAS and MBR sludges suggested that MLSS alone is not a good predictor of sludge dewaterability. Combining CAS and MBR sludges at different proportions generally improved their dewaterability. Combining MBR sludges having typically high MLSS and EPS concentrations with CAS having much lower MLSS concentrations may be an option for full-scale treatment plants experiencing sludge dewaterability problems. Better filterability and higher cake dry solids were achieved with cationic polyelectrolytes compared to anionic and non-ionic ones for all sludge types tested.

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

    Directory of Open Access Journals (Sweden)

    Katrina A. Rieger

    2016-04-01

    Full Text Available 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.

  4. Solid polyelectrolyte fuel cell power supply system; Kotai kobunshigata nenryo denchi dengen system

    Energy Technology Data Exchange (ETDEWEB)

    Aoki, T. [Kanagawa (Japan); Kadoma, H. [Yokohama (Japan); Hashizaki, K.; Tani, T. [Mitsubishi Heavy Industries Ltd., Tokyo (Japan)

    1996-06-11

    When a previous solid polyelectrolyte fuel cell power supply system is used underwater, the water generated by the cell reaction is stored in a water storage tank and it is necessary that the system is suspended in case the generated water is full in the water storage tank to take the system out of water and the water in the tank is discharged in the atmosphere. The solid polyelectrolyte fuel cell power supply system of this invention is equipped with a discharge pump to exhaust the generated water out of the closed vessel accommodating the system or equipped with a device to exhaust the generated water into the outside water accompanied with gushing of high-pressure gas into the outside water. As a result, the water generated by the cell reaction can be exhausted from the system into the outside water at any required time so that the fuel cell power supply system can be operated continuously as far as the supply of the fuel or the oxidizer last. By the installment of this function, a solid polyelectrolyte fuel cell power supply system can be used as an independent underwater power source or as a power source for an underwater moving body. 4 figs.

  5. Densely charged polyelectrolyte-stuffed nanochannel arrays for power generation from salinity gradient

    Science.gov (United States)

    Kwak, Su Hong; Kwon, Seung-Ryong; Baek, Seol; Lim, Seung-Min; Joo, Young-Chang; Chung, Taek Dong

    2016-01-01

    We devised anodized aluminium oxide (AAO) frame-supported polyelectrolytic ion-exchange membranes for the application of electrical power generation systems where salinity differences are present. A series of polyelectrolytic AAO membranes (PAMs) were fabricated as a function of concentration of monomers and cross-linkers. Of the ion-selective PAMs as made, the membranes from the most concentrated monomers and cross-linkers, C-PAM100 and A-PAM100, showed the highest area resistances and permselectivities (the resistances were 4.9 and 2.9 Ω · cm2, the permseletivities for C-PAM100 and A-PAM100 were 99 and 89%, respectively). The measured resistances and permselectivities allowed the power density to be estimated for C-PAM100 and A-PAM100, 3.5 W/m2, and experimentally obtained power density using a reverse electrodialysis (RED) stack was 17.3 mW/m2. In addition, we investigated the influence of an AAO framework on a membrane resistance by comparing the PAMs with polyelectrolyte-stuffed capillaries, revealing that the resistance of the PAM has plenty of potential to be further reduced by optimizing the AAO pore spaces. PMID:27194475

  6. Comparative study of cytotoxicity of ferromagnetic nanoparticles and magnetitecontaining polyelectrolyte microcapsules

    Science.gov (United States)

    Minaeva, O. V.; Brodovskaya, E. P.; Pyataev, M. A.; Gerasimov, M. V.; Zharkov, M. N.; Yurlov, I. A.; Kulikov, O. A.; Kotlyarov, A. A.; Balykova, L. A.; Kokorev, A. V.; Zaborovskiy, A. V.; Pyataev, N. A.; Sukhorukov, G. B.

    2017-01-01

    The cytotoxicity of magnetite nanoparticles (MNP) stabilized with citrate acidand polyelectrolyte multilayer microcapsules containing these particles in the shell is analyzed. Microcapsules were prepared by co-precipitation of iron (II) and (III) chlorides. Polyelectrolyte microcapsules synthesized by the layer-by-layer method from biodegradable polymers polyarginine and dextran sulfate. Cytotoxicity of the synthesized objects was studied on the L929 cells culture and human leucocytes. It was also investigated the phagocytic activity of leukocytes for the MNP and magnetite containing polyelectrolyte microcapsules (MCPM). A set of tests (MTT assay, neutral red uptake assay, lactate dehydrogenase release assay) was used to study the cytotoxicity in vitro. All the tests have shown that the magnetic nanoparticles have a greater cytotoxicity in comparison with microcapsules containing an equivalent amount of magnetite. In contrast to the mouse fibroblast culture, human leukocytes were more resistant to the toxic effects of magnetite. At the concentrations used in our studies no significant reduction in the viability of leukocytes has been registered. Both MNP and MCPM undergo phagocytosis, however, the phagocytic activity of leukocytes for these particles was lower than for the standard objects (latex microparticles).

  7. A small-molecule norspermidine and norspermidine-hosting polyelectrolyte coatings inhibit biofilm formation by multi-species wastewater culture.

    Science.gov (United States)

    Si, Xiurong; Quan, Xiangchun; Wu, Yachuan

    2015-12-01

    Norspermidine is a potent and non-bactericidal small-molecule inhibitor of biofilm growth. In this study, impacts of norspermidine on biofilm control and existing biofilm dispersal by a mixed culture from wastewater treatment systems were investigated. A surface-mediated releasing approach for prevention of bacterial biofilm formation was established via encapsulating norspermidine into polyelectrolyte multilayer coatings. Results showed that the presence of norspermidine (500-1000 μM) in medium remarkably prevented biofilm formation. Norspermidine was also effective in disassembling pre-formed biofilms. Norspermidine-containing multilayer coatings were successfully fabricated on glass slides via layer-by-layer deposition in polyethylenimine (PEI) and poly(acrylic acid) (PAA) solution. This coating exhibited a high anti-biofilm property against a mixed culture and three pure strains (Bacillus subtilis, Pseudomonas aeruginosa, and Escherichia coli). The loading amount and space distribution of norspermidine in the multilayer coating were key factors influencing its anti-biofilm efficacy. The polymer coating with norspermidine loaded in each bilayer (each-layer-type) exhibited better anti-biofilm efficacy than the bottom-type and the top-type coating, which showed a stable biofilm inhibition rate of about 60 % even after 5-day leaching in aqueous solution. Norspermidine could retard bacterial adhesion and destruct biofilm matrix by reducing exopolysaccharides and extracellular DNA (eDNA) associated with bacteria instead of growth inhibition. Norspermidine and the norspermidine-hosting coatings in this study offer a great potential for the control of biofilms in the settings of water purification and wastewater treatment systems, which shows the advantage of broad spectrum and less risk of evolved bacterial resistance compared to conventional microbicidal agents (e.g., antibiotics).

  8. Adsorption of Hydrophobically Modified Polyelectrolytes on Hydrophobic Substrates Adsorption de polyélectrolytes modifiés hydrophobiquement sur les substrats hydrophobes

    Directory of Open Access Journals (Sweden)

    Mays J. W.

    2006-12-01

    Full Text Available A series of diblock copolymers, poly (tert-butyl styrene-sodium poly (styrene sulfonate with different molecular weight and percentage of sulfonation have been used to study the effect of polymer structure on its adsorption behavior onto hydrophobically modified silicon wafers. The percentage of the hydrophobic block varies from 3. 6-8. 9%. Previous studies show that salt concentration is very important for the adsorption of such polyelectrolytes onto silica surfaces. Octadecyltriethoxysilane (OTE has been used to modify the silicon wafer which changes the water contact angle from 50° on unmodified silica to 100° to 120°. On this hydrophobic surface, we found that the adsorption of these slightly hydrophobically modified polyelectrolytes is close to the 4/23rd power of salt concentration predicted by a recent model. The grafting density is also consistent with a dependence on the length of the hydrophobic block to the -12/23rd power, and the length of the polyelectrolyte block to the -6/23rd power, predicted by this model. Une série de copolymères à diblocs poly (tert-butyle styrène-sodium (sulfonate de polystyrène de masses moléculaires et pourcentages de sulfonation différents ont été utilisés pour étudier les effets de la structure du polymère sur son pouvoir d'adsorption sur des surfaces de silicium modifiées hydrophobiquement. Le pourcentage du bloc hydrophobe varie de 3,6 à 8,9%. Les études antérieures montrent que la concentration saline est très importante pour l'adsorption de ces polyélectrolytes sur les surfaces de silice. Nous avons utilisé l'octadecyltriéthoxysilane (OTE pour modifier la surface de silicium qui change l'angle de contact de l'eau de 50° sur la silice non modifiée à une valeur comprise entre 100° et 120° sur la silice modifiée. Sur cette surface hydrophobe, nous constatons que l'adsorption de ces polyélectrolytes légèrement modifiés hydrophobiquement est proche de la loi puissance 4

  9. Coencapsulation of oxygen carriers and glucose oxidase in polyelectrolyte complex capsules for the enhancement of D-gluconic acid and delta-gluconolactone production.

    Science.gov (United States)

    Bucko, Marek; Gemeiner, Peter; Vikartovská, Alica; Mislovicová, Danica; Lacík, Igor; Tkác, Ján

    2010-04-01

    A novel encapsulated oxidative biocatalyst comprising glucose oxidase (GOD) coencapsulated with oxygen carriers within polyelectrolyte complex capsules was developed for the production of D-gluconic acid and delta-gluconolactone. The capsules containing immobilized GOD were produced by polyelectrolyte complexation with sodium alginate (SA) and cellulose sulfate (CS) as polyanions, poly(methylene-co-guanidine) (PMCG) as the polycation, CaCl(2) as the gelling agent and NaCl as the antigelling agent (GOD-SA-CS/PMCG capsules). Poly(dimethylsiloxane) (PDMS) and an emulsion of n-dodecane (DOD) or perfluorodecaline (PFD) with PDMS were used as the oxygen carriers and MnO(2) was used as a hydrogen peroxide decomposition catalyst. Water-soluble PDMS was found to act as both an oxygen carrier and an emulsifier of water-insoluble DOD and PFD. Stable microcapsules could be produced with concentrations of up to 4% (w/w) of PDMS, 10% (w/w) of DOD and PFD, and 25% (w/w) of MnO(2) in the polyanion solution of SA and CS. Roughly a two-fold increase in the GOD activity from 21.0+/-1.1 to 38.4+/-2.0 U*g(-1) and product space-time yields (STY) from 44.3+/-2.0 to 83.4+/-3.4 g*H*day(-1) could be achieved utilizing coencapsulated oxygen carriers compared to GOD encapsulated in the absence of oxygen carriers. This enhanced production does not significantly depend on the selected oxygen carrier under the conditions used in this study.

  10. Adsorption of a linear polyelectrolyte on a gold electrode

    NARCIS (Netherlands)

    Barten, D.; Kleijn, J.M.; Cohen Stuart, M.A.

    2003-01-01

    The adsorption of quaternized poly-2-vinyl pyridine (PVP+), which has a fixed charge per monomer, onto a gold electrode was investigated using reflectometry. The double layer charge and potential of the gold substrate were controlled by means of either the solution pH or by applying an external

  11. Fine tuning of the pH-sensitivity of laponite-doxorubicin nanohybrids by polyelectrolyte multilayer coating.

    Science.gov (United States)

    Xiao, Shili; Castro, Rita; Maciel, Dina; Gonçalves, Mara; Shi, Xiangyang; Rodrigues, João; Tomás, Helena

    2016-03-01

    Despite the wide research done in the field, the development of advanced drug delivery systems with improved drug delivery properties and effective anticancer capability still remains a great challenge. Based on previous work that showed the potentialities of the nanoclay Laponite as a pH-sensitive doxorubicin (Dox) delivery vehicle, herein we report a simple method to modulate its extent of drug release at different pH values. This was achieved by alternate deposition of cationic poly(allylamine) hydrochloride and anionic poly(sodium styrene sulfonate) (PAH/PSS) polyelectrolytes over the surface of Dox-loaded Laponite nanoparticles using the electrostatic layer-by-layer (LbL) self-assembly approach. The successful formation of polyelectrolyte multilayer-coated Dox/Laponite systems was confirmed by Dynamic Light Scattering and zeta potential measurements. Systematic studies were performed to evaluate their drug release profiles and anticancer efficiency. Our results showed that the presence of the polyelectrolyte multilayers improved the sustained release properties of Laponite and allowed a fine tuning of the extension of drug release at neutral and acidic pH values. The cytotoxicity presented by polyelectrolyte multilayer-coated Dox/Laponite systems towards MCF-7 cells was in accordance with the drug delivery profiles. Furthermore, cellular uptake studies revealed that polyelectrolyte multilayer-coated Dox/Laponite nanoparticles can be effectively internalized by cells conducting to Dox accumulation in cell nucleus.

  12. Total Spinal Block after Thoracic Paravertebral Block.

    Science.gov (United States)

    Beyaz, Serbülent Gökhan; Özocak, Hande; Ergönenç, Tolga; Erdem, Ali Fuat; Palabıyık, Onur

    2014-02-01

    Thoracic paravertebral block (TPVB) can be performed with or without general anaesthesia for various surgical procedures. TPVB is a popular anaesthetic technique due to its low side effect profile and high analgesic potency. We used 20 mL of 0.5% levobupivacaine for a single injection of unilateral TPVB at the T7 level with neurostimulator in a 63 year old patient with co-morbid disease who underwent cholecystectomy. Following the application patient lost consciousness, and was intubated. Haemodynamic instability was normalised with rapid volume replacement and vasopressors. Anaesthetic drugs were stopped at the end of the surgery and muscle relaxant was antagonised. Return of mucle strenght was shown with neuromuscular block monitoring. Approximately three hours after TPVB, spontaneous breathing started and consciousness returned. A total spinal block is a rare and life-threatening complication. A total spinal block is a complication of spinal anaesthesia, and it can also occur after peripheral blocks. Clinical presentation is characterised by hypotension, bradicardia, apnea, and cardiac arrest. An early diagnosis and appropriate treatment is life saving. In this case report, we want to present total spinal block after TPVB.

  13. Stabilization of aqueous nanoscale zerovalent iron dispersions by anionic polyelectrolytes: adsorbed anionic polyelectrolyte layer properties and their effect on aggregation and sedimentation

    Energy Technology Data Exchange (ETDEWEB)

    Phenrat, Tanapon; Saleh, Navid [Carnegie Mellon University, Department of Civil and Environmental Engineering (United States); Sirk, Kevin [Carnegie Mellon University, Department of Chemical Engineering (United States); Kim, Hye-Jin [Carnegie Mellon University, Department of Civil and Environmental Engineering (United States); Tilton, Robert D. [Carnegie Mellon University, Department of Chemical Engineering (United States); Lowry, Gregory V. [Carnegie Mellon University, Department of Civil and Environmental Engineering (United States)], E-mail: glowry@cmu.edu

    2008-05-15

    Nanoscale zerovalent iron (NZVI) particles are 5-40 nm sized Fe{sup 0}/Fe-oxide particles that rapidly transform many environmental contaminants to benign products and are a promising in situ remediation agent. Rapid aggregation and limited mobility in water-saturated porous media limits the ability to deliver NZVI dispersions in the subsurface. This study prepares stable NZVI dispersions through physisorption of commercially available anionic polyelectrolytes, characterizes the adsorbed polymer layer, and correlates the polymer coating properties with the ability to prevent rapid aggregation and sedimentation of NZVI dispersions. Poly(styrene sulfonate) with molecular weights of 70 k and 1,000 k g/mol (PSS70K and PSS1M), carboxymethyl cellulose with molecular weights of 90 k and 700 k g/mol (CMC90K and CMC700K), and polyaspartate with molecular weights of 2.5 k and 10 k g/mol (PAP2.5K and 10K) were compared. Particle size distributions were determined by dynamic light scattering during aggregation. The order of effectiveness to prevent rapid aggregation and stabilize the dispersions was PSS70K(83%) > {approx}PAP10K(82%) > PAP2.5K(72%) > CMC700K(52%), where stability is defined operationally as the volume percent of particles that do not aggregate after 1 h. CMC90K and PSS1M could not stabilize RNIP relative to bare RNIP. A similar trend was observed for their ability to prevent sedimentation, with 40, 34, 32, 20, and 5 wt%, of the PSS70K, PAP10K, PAP2.5K, CMC700K, and CMC90K modified NZVI remaining suspended after 7 h of quiescent settling, respectively. The stable fractions with respect to both aggregation and sedimentation correlate well with the adsorbed polyelectrolyte mass and thickness of the adsorbed polyelectrolyte layers as determined by Oshima's soft particle theory. A fraction of the particles cannot be stabilized by any modifier and rapidly agglomerates to micron sized aggregates, as is also observed for unmodified NZVI. This non

  14. Generalized Block Failure

    DEFF Research Database (Denmark)

    Jönsson, Jeppe

    2015-01-01

    Block tearing is considered in several codes as a pure block tension or a pure block shear failure mechanism. However in many situations the load acts eccentrically and involves the transfer of a substantial moment in combination with the shear force and perhaps a normal force. A literature study...... yield lines around the block leads to simple interaction formulas similar to other interaction formulas in the codes.......Block tearing is considered in several codes as a pure block tension or a pure block shear failure mechanism. However in many situations the load acts eccentrically and involves the transfer of a substantial moment in combination with the shear force and perhaps a normal force. A literature study...

  15. Eikonalization of Conformal Blocks

    CERN Document Server

    Fitzpatrick, A Liam; Walters, Matthew T; Wang, Junpu

    2015-01-01

    Classical field configurations such as the Coulomb potential and Schwarzschild solution are built from the $t$-channel exchange of many light degrees of freedom. We study the CFT analog of this phenomenon, which we term the `eikonalization' of conformal blocks. We show that when an operator $T$ appears in the OPE $\\mathcal{O}(x) \\mathcal{O}(0)$, then the large spin $\\ell$ Fock space states $[TT \\cdots T]_{\\ell}$ also appear in this OPE with a computable coefficient. The sum over the exchange of these Fock space states in an $\\langle \\mathcal{O} \\mathcal{O} \\mathcal{O} \\mathcal{O} \\rangle$ correlator build the classical `$T$ field' in the dual AdS description. In some limits the sum of all Fock space exchanges can be represented as the exponential of a single $T$ exchange in the 4-pt correlator of $\\mathcal{O}$. Our results should be useful for systematizing $1/\\ell$ perturbation theory in general CFTs and simplifying the computation of large spin OPE coefficients. As examples we obtain the leading $\\log \\ell$...

  16. Sewage sludge dehydration with biodegradable polyelectrolytes as flocculants. Final report. Pt. 1. Development of synthetic polyelectrolytes; Klaerschlammentwaesserung unter Einsatz biologisch abbaubarer Polyelektrolyte als Flockungshilfsmittel. Abschlussbericht. T. 1. Entwicklung der synthetischen Polyelektrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Matuschewski, H.; Gohlke, U.; Jaeger, W.

    1997-09-01

    Polyelectrolytes with improved degradability were to be developed for dehydration of uncontaminated sewage sludge. Part-project I investigated the synthesis of polymers. For this purpose, polyvinyl alcohol was functionalized into polyelectrolytes by etheration, Mannich reaction, acetalisation and graft copolymerisation. Some of the new polymers have very good flocculation and dehydration characteristics. (SR) [Deutsch] Ziel des Vorhabens war es, Ergebnisse zur Entwaesserung nicht kontaminierter Klaerschlaemme mit Polyelektrolyten mit verbesserter Abbaubarkeit zu erarbeiten. Ziel des Teilvorhabens I war die Synthese entsprechender Polymerer. Dazu wurde Polyvinylalkohol durch Veretherung, Mannichreaktion, Acetalisierung und Propfcopolymerisation zu Polyelektrolyten funktionalisiert. Die neuen Polymere weisen zum Teil sehr gute Flockungs- und Entwaesserungseigenschaften auf. (SR)

  17. BLOCK H-MATRICES AND SPECTRUM OF BLOCK MATRICES

    Institute of Scientific and Technical Information of China (English)

    黄廷祝; 黎稳

    2002-01-01

    The block H-matrices are studied by the concept of G-functions, several concepts of block matrices are introduced. Equivalent characters of block H-matrices are obtained. Spectrum localizations claracterized by Gfunctions for block matrices are got.

  18. Complex coacervation: A field theoretic simulation study of polyelectrolyte complexation

    Science.gov (United States)

    Lee, Jonghoon; Popov, Yuri O.; Fredrickson, Glenn H.

    2008-06-01

    Using the complex Langevin sampling strategy, field theoretic simulations are performed to study the equilibrium phase behavior and structure of symmetric polycation-polyanion mixtures without salt in good solvents. Static structure factors for the segment density and charge density are calculated and used to study the role of fluctuations in the electrostatic and chemical potential fields beyond the random phase approximation. We specifically focus on the role of charge density and molecular weight on the structure and complexation behavior of polycation-polyanion solutions. A demixing phase transition to form a ``complex coacervate'' is observed in strongly charged systems, and the corresponding spinodal and binodal boundaries of the phase diagram are investigated.

  19. Block TERM factorization of block matrices

    Institute of Scientific and Technical Information of China (English)

    SHE Yiyuan; HAO Pengwei

    2004-01-01

    Reversible integer mapping (or integer transform) is a useful way to realize Iossless coding, and this technique has been used for multi-component image compression in the new international image compression standard JPEG 2000. For any nonsingular linear transform of finite dimension, its integer transform can be implemented by factorizing the transform matrix into 3 triangular elementary reversible matrices (TERMs) or a series of single-row elementary reversible matrices (SERMs). To speed up and parallelize integer transforms, we study block TERM and SERM factorizations in this paper. First, to guarantee flexible scaling manners, the classical determinant (det) is generalized to a matrix function, DET, which is shown to have many important properties analogous to those of det. Then based on DET, a generic block TERM factorization,BLUS, is presented for any nonsingular block matrix. Our conclusions can cover the early optimal point factorizations and provide an efficient way to implement integer transforms for large matrices.

  20. In situ monitoring of the formation of nanoscale polyelectrolyte coatings on optical fibers using Surface Plasmon Resonances.

    Science.gov (United States)

    Shevchenko, Yanina; Ahamad, Nur Uddin; Ianoul, Anatoli; Albert, Jacques

    2010-09-13

    Deposition of a conformal nanoscale polymer coating was characterized using a fiber SPR sensor. The sensor platform consisted of an unmodified gold-coated single mode fiber where SPR was excited through the coupling of the core mode into the cladding modes using a Tilted Fiber Bragg Grating. The results from this study show how the sensor can monitor in real time the formation of polyelectrolyte coatings during a process consisting of several stages of immersion. The experimental data was further calibrated by simulations and Atomic Force Microscope imaging allowing us to determine the thickness and refractive index of the adsorbed polyelectrolyte.