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Sample records for dynamics determine polyelectrolyte

  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. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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)

  7. 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.

  8. Adsorption of tannic acid on polyelectrolyte monolayers determined in situ by streaming potential measurements.

    Science.gov (United States)

    Oćwieja, M; Adamczyk, Z; Morga, M

    2015-01-15

    Physicochemical characteristics of tannic acid (tannin) suspensions comprising its stability for a wide range of ionic strength and pH were thoroughly investigated using UV-vis spectrophotometry, dynamic light scattering and microelectrophoretic measurements. These studies allowed to determine the hydrodynamic diameter of the tannic acid that was 1.63 nm for the pH range 3.5-5.5. For pH above 6.0 the hydrodynamic diameter significantly decreased as a result of the tannin hydrolysis. The electrophoretic mobility measurements confirmed that tannic acid is negatively charged for these values of pH and ionic strength 10(-4)-10(-2) M. Therefore, in order to promote adsorption of tannin molecules on negatively charged mica, the poly(allylamine hydrochloride) (PAH) supporting monolayers were first adsorbed under diffusion transport conditions. The coverage of polyelectrolyte monolayers was regulated by changing bulk concentration of PAH and the adsorption time. The electrokinetic characteristics of bare and PAH-covered mica were determined using the streaming potential measurements. The zeta potential of these PAH monolayers was highly positive, equal to 46 mV for ionic strength of 10(-2) M. The kinetics of tannin adsorption on these PAH supporting monolayers was evaluated by the in situ the streaming potential measurements. The zeta potential of PAH monolayers abruptly decreases with the adsorption of tannin molecules that was quantitatively interpreted in terms of the three-dimensional electrokinetic model. The acid-base characteristics of tannin monolayers were acquired via the streaming potential measurements for a broad range of pH. The obtained results indicate that it is possible to control adsorption of tannin on positively charged surfaces in order to designed new multilayer structures of desirable electrokinetic properties and stability.

  9. 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.

  10. 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...

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

    Science.gov (United States)

    Hoda, Nazish; Kumar, Satish

    2007-12-21

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

  12. Dynamics of polyelectrolyte adsorption and colloidal flocculation upon mixing studied using mono-dispersed polystyrene latex particles

    NARCIS (Netherlands)

    Feng, Lili; Cohen Stuart, Martien; Adachi, Yasuhisa

    2015-01-01

    The dynamic behavior of polyelectrolytes just after their encounter with the surface of bare colloidal particles is analyzed, using the flocculation properties of mono-dispersed polystyrene latex (PSL) particles. Applying a Standardized Colloid Mixing (SCM) approach, effects of ionic strength and

  13. Dynamic XPS measurements of ultrathin polyelectrolyte films containing antibacterial Ag–Cu nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Taner-Camcı, Merve; Suzer, Sefik, E-mail: suzer@fen.bilkent.edu.tr [Department of Chemistry, Bilkent University, 06800 Ankara (Turkey)

    2014-03-15

    Ultrathin films consisting of polyelectrolyte layers prepared by layer-by-layer deposition technique and containing also Ag and Cu nanoparticles exhibit superior antibacterial activity toward Escherichia coli. These films have been investigated with XPS measurements under square wave excitation at two different frequencies, in order to further our understanding about the chemical/physical nature of the nanoparticles. Dubbed as dynamical XPS, such measurements bring out similarities and differences among the surface structures by correlating the binding energy shifts of the corresponding XPS peaks. Accordingly, it is observed that the Cu2p, Ag3d of the metal nanoparticles, and S2p of cysteine, the stabilizer and the capping agent, exhibit similar shifts. On the other hand, the C1s, N1s, and S2p peaks of the polyelectrolyte layers shift differently. This finding leads us the claim that the Ag and Cu atoms are in a nanoalloy structure, capped with cystein, as opposed to phase separated entities.

  14. 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.

  15. 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.

  16. 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

  17. 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....

  18. 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

  19. 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.

  20. 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.

  1. The local dynamics of unfolded versus folded tRNA in comparison to synthetic polyelectrolytes and the role of electrostatic interactions

    Science.gov (United States)

    Roh, Joon Ho; Tyagi, Madhu; Briber, Robert M.; Woodson, Sarah A.; Sokolov, Alexei

    2012-02-01

    The local dynamics of RNA is strongly coupled to biological functions such as ligand recognition and catalysis. We have used quasielastic neutron scattering spectroscopy to follow the local motion of RNA and a synthetic polyelectrolyte as a function of Mg2+ concentration. We have observed that increasing Mg+2 concentration increases the picosecond to nanosecond dynamics of hydrated tRNA while stabilizing the tRNA folded structure. Analyses of the atomic mean-squared displacement, relaxation time, persistence length, and fraction of mobile atoms showed that unfolded tRNA is more rigid than in the folded state. This same behavior was observed for sulfonated polystyrene indicating that the increased dynamics in arises from charge screening of the polyelectrolyte rather than specific interactions. These results are opposite to what is observed for proteins for the relationship between the unfolded/folded states and the internal dynamics where the folded state is observed to be more rigid than the unfolded state. We conclude that the local dynamics for both bio- and synthetic polymers are strongly influenced by the electrostatic environment.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. Molecular Dynamics Simulation for the Effect of Chain Length of Spacer and Tail of Cationic Gemini Surfactant on the Complex with Anionic Polyelectrolyte%连接基团与尾链长度对阳离子Gemini表面活性剂与阴离子聚电解质复合物影响的分子动力学模拟

    Institute of Scientific and Technical Information of China (English)

    徐毅; 冯剑; 尚亚卓; 刘洪来

    2007-01-01

    Interaction of anionic polyelectrolyte with cationic gemini surfactant has been investigated by coarse-grained molecular dynamics simulation. Polyelectrolyte facilitates the oppositely charged ionic surfactants to aggregate by suppressing the electrostatic repulsion between ionic head groups leading to the formation of micellar complex. With addition of surfactant, the conformation of polyion chain changes from stretched to random coiled to spherical, and at the same time more free micelles are formed by surfactants in mixtures. Increasing the length of spacer or tail chain in gemini surfactant will weaken its interaction with polyelectrolyte and simultaneously strengthen its tendency to self-assemble. The simulation results are consistent with experimental observations and reveal that the electrostatic interaction plays an important role in the interaction of polyelectrolyte with gemini surfactant.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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).

  14. 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."

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Simultaneous determination of protein structure and dynamics

    DEFF Research Database (Denmark)

    Lindorff-Larsen, Kresten; Best, Robert B.; DePristo, M. A.

    2005-01-01

    We present a protocol for the experimental determination of ensembles of protein conformations that represent simultaneously the native structure and its associated dynamics. The procedure combines the strengths of nuclear magnetic resonance spectroscopy-for obtaining experimental information at ...

  20. 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

  1. 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).

  2. Polyelectrolyte surfactant aggregates and their deposition on macroscopic surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Voisin, David

    2002-07-01

    the CSC have been determined for mixtures of cationically modified guar gums (of varying charge density) with two anionic surfactants: sodium lauryl (or dodecyl) ether sulfate [SLES] and sodium dodecyl sulfate [SDS], for various concentrations of the polyelectrolyte and added sodium chloride, at room temperature. The addition of sodium chloride has only a minor net effect on the CFC, but increases the CSC significantly. The interactions between the cationic polyelectrolyte and the surfactant have been studied in the one-phase regions, i.e. below the CFC and above the CSC, using different techniques. Surface tension, electrophoresis, light scattering and viscosimetry have been employed. In the two-phase region, the sedimented floe phase has been analysed and the flocculation has been investigated. Rheology of the floe phase has been studied, after a mild compression by centrifugation. The initial rate of flocculation has been determined, using stop-flow equipment. The growth and the structure of the flocs have been investigated by light scattering. The open-network flocs of polyelectrolyte-surfactant particles grow to {approx}10's {mu}m in size, prior to their eventual settling out. Other colloidal particles can be trapped within these large flocs, and the flocs can be used to transport these particles to a macroscopic surface. The deposition and the removal of such composite flocs on glass surfaces, under flow, have been studied using a flow cell device coupled with an optical microscope. Scanning electron microscopy and atomic force microscopy have also been employed. (author)

  3. 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.

  4. Variability in primary productivity determines metapopulation dynamics.

    Science.gov (United States)

    Fernández, Néstor; Román, Jacinto; Delibes, Miguel

    2016-04-13

    Temporal variability in primary productivity can change habitat quality for consumer species by affecting the energy levels available as food resources. However, it remains unclear how habitat-quality fluctuations may determine the dynamics of spatially structured populations, where the effects of habitat size, quality and isolation have been customarily assessed assuming static habitats. We present the first empirical evaluation on the effects of stochastic fluctuations in primary productivity--a major outcome of ecosystem functions--on the metapopulation dynamics of a primary consumer. A unique 13-year dataset from an herbivore rodent was used to test the hypothesis that inter-annual variations in primary productivity determine spatiotemporal habitat occupancy patterns and colonization and extinction processes. Inter-annual variability in productivity and in the growing season phenology significantly influenced habitat colonization patterns and occupancy dynamics. These effects lead to changes in connectivity to other potentially occupied habitat patches, which then feed back into occupancy dynamics. According to the results, the dynamics of primary productivity accounted for more than 50% of the variation in occupancy probability, depending on patch size and landscape configuration. Evidence connecting primary productivity dynamics and spatiotemporal population processes has broad implications for metapopulation persistence in fluctuating and changing environments.

  5. 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.

  6. Fermion Determinant with Dynamical Chiral Symmetry Breaking

    Institute of Scientific and Technical Information of China (English)

    LU Qin; YANG Hua; WANG Qing

    2002-01-01

    One-loop fermion determinant is discussed for the case in which the dynamical chiral symmetry breakingcaused by momentum-dependent fermion self-energy ∑(p2) takes place. The obtained series generalizes the heat kernelexpansion for hard fermion mass.

  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. Simultaneous determination of protein structure and dynamics

    DEFF Research Database (Denmark)

    Lindorff-Larsen, Kresten; Best, Robert B.; DePristo, M. A.

    2005-01-01

    We present a protocol for the experimental determination of ensembles of protein conformations that represent simultaneously the native structure and its associated dynamics. The procedure combines the strengths of nuclear magnetic resonance spectroscopy-for obtaining experimental information...... at the atomic level about the structural and dynamical features of proteins-with the ability of molecular dynamics simulations to explore a wide range of protein conformations. We illustrate the method for human ubiquitin in solution and find that there is considerable conformational heterogeneity throughout...... the protein structure. The interior atoms of the protein are tightly packed in each individual conformation that contributes to the ensemble but their overall behaviour can be described as having a significant degree of liquid-like character. The protocol is completely general and should lead to significant...

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. Noise and determinism in synchronized sheep dynamics

    Science.gov (United States)

    Grenfell, B. T.; Wilson, K.; Finkenstädt, B. F.; Coulson, T. N.; Murray, S.; Albon, S. D.; Pemberton, J. M.; Clutton-Brock, T. H.; Crawley, M. J.

    1998-08-01

    A major debate in ecology concerns the relative importance of intrinsic factors and extrinsic environmental variations in determining population size fluctuations. Spatial correlation of fluctuations in different populations caused by synchronous environmental shocks,, is a powerful tool for quantifying the impact of environmental variations on population dynamics,. However, interpretation of synchrony is often complicated by migration between populations,. Here we address this issue by using time series from sheep populations on two islands in the St Kilda archipelago. Fluctuations in the sizes of the two populations are remarkably synchronized over a 40-year period. A nonlinear time-series model shows that a high and frequent degree of environmental correlation is required to achieve this level of synchrony. The model indicates that if there were less environmental correlation, population dynamics would be much less synchronous than is observed. This is because of a threshold effect that is dependent on population size; the threshold magnifies random differences between populations. A refined model showsthat part of the required environmental synchronicity can be accounted for by large-scale weather variations. These results underline the importance of understanding the interaction between intrinsic and extrinsic influences on population dynamics.

  17. 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.

  18. 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...

  19. 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.

  20. 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.

  1. Determining gastric cancer resectability by dynamic MDCT

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Zilai; Zhang, Huan; Du, Lianjun; Ding, Bei; Song, Qi; Ling, Huawei; Huang, Baisong; Chen, Kemin [Jiaotong University, Department of Radiology, Shanghai (China); Yan, Chao [Jiaotong University, Department of Surgery, Shanghai (China)

    2010-03-15

    Multi-detector row CT (MDCT) has been widely used to detect primary lesions and to evaluate TNM staging. In this study we evaluated the accuracy of dynamic MDCT in the preoperative determination of the resectability of gastric cancer. MDCT was used to image 350 cases of gastric cancer diagnosed by biopsy before surgery. MDCT findings regarding TNM staging and resectability were correlated with surgical and pathological findings. The accuracy of MDCT for staging gastric cancer was high, especially for tumour stage T1 (94.3%), lymph node stage N2 (87.3%), and for predicting distant metastases (>96.6%). When resectability was considered to be the outcome, the total accuracy of MDCT was 87.4%, sensitivity was 89.7% and specificity was 76.7%. Results showed high sensitivity for identifying peritoneal seeding (90.0%) and for predicting liver metastasis (80.0%). Dynamic enhanced MDCT is useful for TNM staging of gastric cancers and for predicting tumour respectability preoperatively. (orig.)

  2. 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...

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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…

  8. 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.

  9. 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.

  10. Functional finishing of aminated polyester using biopolymer-based polyelectrolyte microgels.

    Science.gov (United States)

    Glampedaki, Pelagia; Dutschk, Victoria; Jocic, Dragan; Warmoeskerken, Marijn M C G

    2011-10-01

    This study focuses on a microgel-based functionalization method applicable to polyester textiles for improving their hydrophilicity and/or moisture-management properties, eventually enhancing wear comfort. The method proposed aims at achieving pH-/temperature-controlled wettability of polyester within a physiological pH/temperature range. First, primary amine groups are created on polyester surfaces using ethylenediamine; second, biopolymer-based polyelectrolyte microgels are incorporated using the natural cross-linker genipin. The microgels consist of the pH-responsive natural polysaccharide chitosan and pH/thermoresponsive poly(N-isopropylacrylamide-co-acrylic acid) microparticles. Scanning electron microscopy confirmed the microgel presence on polyester surfaces. X-ray photoelectron spectroscopy revealed nitrogen concentration, supporting increased microscopy results. Electrokinetic analysis showed that functionalized polyester surfaces have a zero-charge point at pH 6.5, close to the microgel isoelectric point. Dynamic wetting measurements revealed that functionalized polyester has shorter total water absorption time than the reference. This absorption time is also pH dependent, based on dynamic contact angle and micro-roughness measurements, which indicated microgel swelling at different pH values. Furthermore, at 40 °C functionalized polyester has higher vapor transmission rates than the reference, even at high relative humidity. This was attributed to the microgel thermoresponsiveness, which was confirmed through the almost 50% decrease in microparticle size between 20 and 40 °C, as determined by dynamic light scattering measurements.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Determinants of Price Dynamics in Ethiopia

    African Journals Online (AJOL)

    the National bank of Ethiopia exercised tight monetary and fiscal policy, which in .... to apply standard estimation or testing procedures in a dynamic time series model, it is ... and SC indicate that lag order of two is appropriate for the model.

  16. 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.

  17. 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.

  18. 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.

  19. 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...

  20. 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.

  1. 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

  2. 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.

  3. Determinants of Welfare Dynamics in Rural Nicaragua

    DEFF Research Database (Denmark)

    Jakobsen, Kristian Thor

    2011-01-01

    This article explores the determinants of poverty movements in rural Nicaragua by introducing a bivariate probate model, making it possible to treat the initial state of poverty as endogenous and thus avoiding introducing selection bias. The results indicate that this is relevant when exploring...... in explaining poverty movements. Moreover, climate-related shocks such as droughts and pest attacks not only have persistent and adverse impacts on household consumption, but also affect households’ productive asset holdings, which could affect their income-generating potential in the longer term....

  4. 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.

  5. 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

  6. 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

  7. 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

  8. 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

  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. 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.

  11. 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.

  12. 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.

  13. 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.

  14. A stochastic phase-field model determined from molecular dynamics

    KAUST Repository

    von Schwerin, Erik

    2010-03-17

    The dynamics of dendritic growth of a crystal in an undercooled melt is determined by macroscopic diffusion-convection of heat and by capillary forces acting on the nanometer scale of the solid-liquid interface width. Its modelling is useful for instance in processing techniques based on casting. The phase-field method is widely used to study evolution of such microstructural phase transformations on a continuum level; it couples the energy equation to a phenomenological Allen-Cahn/Ginzburg-Landau equation modelling the dynamics of an order parameter determining the solid and liquid phases, including also stochastic fluctuations to obtain the qualitatively correct result of dendritic side branching. This work presents a method to determine stochastic phase-field models from atomistic formulations by coarse-graining molecular dynamics. It has three steps: (1) a precise quantitative atomistic definition of the phase-field variable, based on the local potential energy; (2) derivation of its coarse-grained dynamics model, from microscopic Smoluchowski molecular dynamics (that is Brownian or over damped Langevin dynamics); and (3) numerical computation of the coarse-grained model functions. The coarse-grained model approximates Gibbs ensemble averages of the atomistic phase-field, by choosing coarse-grained drift and diffusion functions that minimize the approximation error of observables in this ensemble average. © EDP Sciences, SMAI, 2010.

  15. Determining of the CME dynamics by digital image

    Science.gov (United States)

    Rigozo, Nivaor R.; Dal Lago, Alisson; Schuch, Nelson Jorge

    We have developed a new technique to detection of Coronal Mass Eject (CME) by used image processing. This is technique permit determined the CME dynamic (distance, velocity and acceleration radial, and distance, velocity and acceleration expansion). The CME dynamic is determined by selection a direction radial in a given LASCO image, which starts just before the occulter (close to the center) and extends to the extremity of the image. By tacking a series of image and extracting the same direction radial, for each of them and placing them side by side. It is possible to have a time history of any moving feature inside this direction. This technique allows you to choose the number of directions that will be used in CME detecting, i.e., in determining its dynamics.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. Factors Determining Particle Dynamics over the Air-Sea Interface

    NARCIS (Netherlands)

    Leeuw, G. de; Larsen, S.E.; Mestayer, P.G.

    2000-01-01

    Work done in the framework of the ASE subproject, topic 5, on factors determining particle dynamics over the air-sea interface, is briefly reviewed. Emphasis is on the cooperative efforts between the authors, covering a period of roughly 8 years, from 1988 until 1996 [1–16], which in part were

  6. 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

  7. Polyelectrolyte Threading through a Nanopore

    Directory of Open Access Journals (Sweden)

    Pai-Yi Hsiao

    2016-03-01

    Full Text Available Threading charged polymers through a nanopore, driven by electric fields E, is investigated by means of Langevin dynamics simulations. The mean translocation time 〈 τ 〉 is shown to follow a scaling law Nα, and the exponent α increases monotonically from 1.16 (4 to 1.40 (3 with E. The result is double-checked by the calculation of mean square displacement of translocation coordinate, which asserts a scaling behavior tβ (for t near τ with β complying with the relation αβ = 2. At a fixed chain length N, 〈τ〉 displayed a reciprocal scaling behavior E−1 in the weak and also in the strong fields, connected by a transition E−1.64(5 in the intermediate fields. The variations of the radius of gyration of chain and the positions of chain end are monitored during a translocation process; far-from-equilibrium behaviors are observed when the driving field is strong. A strong field can strip off the condensed ions on the chain when it passes the pore. The total charges of condensed ions are hence decreased. The studies for the probability and density distributions reveal that the monomers in the trans-region are gathered near the wall and form a pancake-like density profile with a hump cloud over it in the strong fields, due to fast translocation.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. INDIRECT DETERMINATION METHOD OF DYNAMIC FORCEBY USING CEPSTRUM ANALYSIS

    Institute of Scientific and Technical Information of China (English)

    吴淼; 魏任之

    1996-01-01

    The dynamic load spectrum is one of the most important basis of design and dynamic characteristics analysis of machines. But it is difficult to measure it on many occasions, especially for mining machines, due to their bad working circumstances and high cost of measurements. For such situation, the load spectrum has to be obtained by indirect determination methods. A new method to identify the load spectrum, cepstrum analysis method, was presented in this paper.This method can be used to eliminate the filtering influence of transfer function to the response signals so that the load spectrum can be determined indirectly. The experimental and engineering actual examples indicates that this method has the advantages that the calculation is simple and the measurement is easy.

  13. Satellite Aerodynamics and Density Determination from Satellite Dynamic Response

    Science.gov (United States)

    Karr, G. R.

    1972-01-01

    The aerodynamic drag and lift properties of a satellite are first expressed as a function of two parameters associated with gas-surface interaction at the satellite surface. The dynamic response of the satellite as it passes through the atmosphere is then expressed as a function of the two gas-surface interaction parameters, the atmospheric density, the satellite velocity, and the satellite orientation to the high speed flow. By proper correlation of the observed dynamic response with the changing angle of attack of the satellite, it is found that the two unknown gas-surface interaction parameters can be determined. Once the gas-surface interaction parameters are known, the aerodynamic properties of the satellite at all angles of attack are also determined.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Comprehensive Gravity and Dynamics Model Determination of Binary Asteroid Systems

    Science.gov (United States)

    Fahnestock, Eugene G.

    2009-09-01

    I present the development of additional tools within the framework of JPL's in-house Mirage / Orbit Determination Program (ODP) software to allow the determination of a comprehensive gravity and dynamics model for any binary asteroid system potentially visited by a spacecraft rendezvous mission. This involves a concurrent global solution for the gravity fields of both components, sufficient parametric description of their fully-coupled translational and rotational dynamics, the spacecraft state, and all other relevant force model parameters. This estimation process primarily uses spacecraft radio tracking data (range and Doppler measurements), supplemented by in-situ imaging observations data types. A solution for the gravity field (gravity analysis) and a simultaneous solution for the spacecraft motion and other system properties has been performed before using the ODP for solitary irregular small solar system bodies (e.g. Eros, visited by the NEAR mission), but never for any closely gravitationally bound pair of irregular small solar system bodies. I am expanding NASA's tool set to allow the latter, in preparation for potential future spacecraft rendezvous missions. This is nontrivial, because of the need to incorporate propagation of the binary system's fully-coupled rigid-body dynamical model either along with the spacecraft state within Mirage/ODP or "offline", followed by interpolating an appropriate "binary dynamics ephemeris” representation. Further, this model optionally incorporates formulations for body gravity fields not previously used in this context, and it can be computationally very expensive. However, successfully performing this model determination at a binary asteroid yields valuable science results concerning internal mass distributions and structures of the components and insight into the system's formation and evolution. In this poster I present my current progress in the development of this capability and results for the quality of science

  19. 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

  20. A system dynamics model to determine products mix

    Directory of Open Access Journals (Sweden)

    Mahtab Hajghasem

    2014-02-01

    Full Text Available This paper presents an implementation of system dynamics model to determine appropriate product mix by considering various factors such as labor, materials, overhead, etc. for an Iranian producer of cosmetic and sanitary products. The proposed model of this paper considers three hypotheses including the relationship between product mix and profitability, optimum production capacity and having minimum amount of storage to take advantage of low cost production. The implementation of system dynamics on VENSIM software package has confirmed all three hypotheses of the survey and suggested that in order to reach better mix product, it is necessary to reach optimum production planning, take advantage of all available production capacities and use inventory management techniques.

  1. Clustering determines the dynamics of complex contagions in multiplex networks

    CERN Document Server

    Zhuang, Yong; Yağan, Osman

    2016-01-01

    We present the mathematical analysis of generalized complex contagions in clustered multiplex networks for susceptible-infected-recovered (SIR)-like dynamics. The model is intended to understand diffusion of influence, or any other spreading process implying a threshold dynamics, in setups of interconnected networks with significant clustering. The contagion is assumed to be general enough to account for a content-dependent linear threshold model, where each link type has a different weight (for spreading influence) that may depend on the content (e.g., product, rumor, political view) that is being spread. Using the generating functions formalism, we determine the conditions, probability, and expected size of the emergent global cascades. This analysis provides a generalization of previous approaches and is specially useful in problems related to spreading and percolation. The results present non trivial dependencies between the clustering coefficient of the networks and its average degree. In particular, sev...

  2. 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'.

  3. 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

  4. 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...

  5. 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.

  6. Clustering determines the dynamics of complex contagions in multiplex networks

    Science.gov (United States)

    Zhuang, Yong; Arenas, Alex; Yaǧan, Osman

    2017-01-01

    We present the mathematical analysis of generalized complex contagions in a class of clustered multiplex networks. The model is intended to understand spread of influence, or any other spreading process implying a threshold dynamics, in setups of interconnected networks with significant clustering. The contagion is assumed to be general enough to account for a content-dependent linear threshold model, where each link type has a different weight (for spreading influence) that may depend on the content (e.g., product, rumor, political view) that is being spread. Using the generating functions formalism, we determine the conditions, probability, and expected size of the emergent global cascades. This analysis provides a generalization of previous approaches and is especially useful in problems related to spreading and percolation. The results present nontrivial dependencies between the clustering coefficient of the networks and its average degree. In particular, several phase transitions are shown to occur depending on these descriptors. Generally speaking, our findings reveal that increasing clustering decreases the probability of having global cascades and their size, however, this tendency changes with the average degree. There exists a certain average degree from which on clustering favors the probability and size of the contagion. By comparing the dynamics of complex contagions over multiplex networks and their monoplex projections, we demonstrate that ignoring link types and aggregating network layers may lead to inaccurate conclusions about contagion dynamics, particularly when the correlation of degrees between layers is high.

  7. Determination of dynamic fracture toughness using a new experimental technique

    Directory of Open Access Journals (Sweden)

    Cady Carl M.

    2015-01-01

    Full Text Available In other studies dynamic fracture toughness has been measured using Charpy impact and modified Hopkinson Bar techniques. In this paper results will be shown for the measurement of fracture toughness using a new test geometry. The crack propagation velocities range from ∼0.15 mm/s to 2.5 m/s. Digital image correlation (DIC will be the technique used to measure both the strain and the crack growth rates. The boundary of the crack is determined using the correlation coefficient generated during image analysis and with interframe timing the crack growth rate and crack opening can be determined. A comparison of static and dynamic loading experiments will be made for brittle polymeric materials. The analysis technique presented by Sammis et al. [1] is a semi-empirical solution, however, additional Linear Elastic Fracture Mechanics analysis of the strain fields generated as part of the DIC analysis allow for the more commonly used method resembling the crack tip opening displacement (CTOD experiment. It should be noted that this technique was developed because limited amounts of material were available and crack growth rates were to fast for a standard CTOD method.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  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. Multiscale Modeling of Dendrimers and Their Interactions with Bilayers and Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Ronald G. Larson

    2009-01-01

    Full Text Available Recent advances in molecular dynamics simulation methodologies and computational power have allowed accurate predictions of dendrimer size, shape, and interactions with bilayers and polyelectrolytes with modest computational effort. Atomistic and coarse-grained (CG models show strong interactions of cationic dendrimers with lipid bilayers. The CG simulations with explicit lipid and water capture bilayer penetration and pore formation, showing that pore formation is enhanced at high dendrimer concentration, but suppressed at low temperature and high salt concentration, in agreement with experiments. Cationic linear polymers have also been simulated, but do not perforate membranes, evidently because by deforming into a pancake, the charges on a linear polymer achieve intimate contact with a single bilayer leaflet. The relatively rigid dendrimers, on the other hand, penetrate the bilayer, because only by interacting with both leaflets can they achieve a similar degree of contact between charged groups. Also, a “dendrimer-filled vesicle” structure for the dendrimer-membrane interaction is predicted by mesoscale thermodynamic simulations, in agreement with a picture derived from experimental observations. In simulations of complexes of dendrimer and polyelectrolyte, anionic linear chains wrap around the cationic dendrimer and penetrate inside it. Overall, these new results indicate that simulations can now provide predictions in excellent agreement with experimental observations, and provide atomic-scale insights into dendrimer structure and dynamics.

  14. pH and Salt Effects on the Associative Phase Separation of Oppositely Charged Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Prateek K. Jha

    2014-05-01

    Full Text Available The classical Voorn-Overbeek thermodynamic theory of complexation and phase separation of oppositely charged polyelectrolytes is generalized to account for the charge accessibility and hydrophobicity of polyions, size of salt ions, and pH variations. Theoretical predictions of the effects of pH and salt concentration are compared with published experimental data and experiments we performed, on systems containing poly(acrylic acid (PAA as the polyacid and poly(N,N-dimethylaminoethyl methacrylate (PDMAEMA or poly(diallyldimethyl ammonium chloride (PDADMAC as the polybase. In general, the critical salt concentration below which the mixture phase separates, increases with degree of ionization and with the hydrophobicity of polyelectrolytes. We find experimentally that as the pH is decreased below 7, and PAA monomers are neutralized, the critical salt concentration increases, while the reverse occurs when pH is raised above 7. We predict this asymmetry theoretically by introducing a large positive Flory parameter (= 0.75 for the interaction of neutral PAA monomers with water. This large positive Flory parameter is supported by molecular dynamics simulations, which show much weaker hydrogen bonding between neutral PAA and water than between charged PAA and water, while neutral and charged PDMAEMA show similar numbers of hydrogen bonds. This increased hydrophobicity of neutral PAA at reduced pH increases the tendency towards phase separation despite the reduction in charge interactions between the polyelectrolytes. Water content and volume of coacervate are found to be a strong function of the pH and salt concentration.

  15. 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.

  16. 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...

  17. Determining habitat quality for species that demonstrate dynamic habitat selection

    Science.gov (United States)

    Beerens, James; Frederick, Peter C; Noonburg, Erik G; Gawlik, Dale E.

    2015-01-01

    Determining habitat quality for wildlife populations requires relating a species' habitat to its survival and reproduction. Within a season, species occurrence and density can be disconnected from measures of habitat quality when resources are highly seasonal, unpredictable over time, and patchy. Here we establish an explicit link among dynamic selection of changing resources, spatio-temporal species distributions, and fitness for predictive abundance and occurrence models that are used for short-term water management and long-term restoration planning. We used the wading bird distribution and evaluation models (WADEM) that estimate (1) daily changes in selection across resource gradients, (2) landscape abundance of flocks and individuals, (3) conspecific foraging aggregation, and (4) resource unit occurrence (at fixed 400 m cells) to quantify habitat quality and its consequences on reproduction for wetland indicator species. We linked maximum annual numbers of nests detected across the study area and nesting success of Great Egrets (Ardea alba), White Ibises (Eudocimus albus), and Wood Storks (Mycteria americana) over a 20-year period to estimated daily dynamics of food resources produced by WADEM over a 7490 km2 area. For all species, increases in predicted species abundance in March and high abundance in April were strongly linked to breeding responses. Great Egret nesting effort and success were higher when birds also showed greater conspecific foraging aggregation. Synthesis and applications: This study provides the first empirical evidence that dynamic habitat selection processes and distributions of wading birds over environmental gradients are linked with reproductive measures over periods of decades. Further, predictor variables at a variety of temporal (daily-multiannual) resolutions and spatial (400 m to regional) scales effectively explained variation in ecological processes that change habitat quality. The process used here allows managers to develop

  18. Determining equilibrium constants for dimerization reactions from molecular dynamics simulations.

    Science.gov (United States)

    De Jong, Djurre H; Schäfer, Lars V; De Vries, Alex H; Marrink, Siewert J; Berendsen, Herman J C; Grubmüller, Helmut

    2011-07-15

    With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices covers sufficiently many dimerization and dissociation events, their binding free energy is readily derived from the fraction of time during which the two helices are observed in dimeric form. Exactly how the correct value for the free energy is to be calculated, however, is unclear, and indeed several different and contradictory approaches have been used. In particular, results obtained via Boltzmann statistics differ from those determined via the law of mass action. Here, we develop a theory that resolves this discrepancy. We show that for simulation systems containing two molecules, the dimerization free energy is given by a formula of the form ΔG ∝ ln(P(1) /P(0) ). Our theory is also applicable to high concentrations that typically have to be used in molecular dynamics simulations to keep the simulation system small, where the textbook dilute approximations fail. It also covers simulations with an arbitrary number of monomers and dimers and provides rigorous error estimates. Comparison with test simulations of a simple Lennard Jones system with various particle numbers as well as with reference free energy values obtained from radial distribution functions show full agreement for both binding free energies and dimerization statistics.

  19. Determination of Reference Chemical Potential Using Molecular Dynamics Simulations

    Directory of Open Access Journals (Sweden)

    Krishnadeo Jatkar

    2010-01-01

    Full Text Available A new method implementing molecular dynamics (MD simulations for calculating the reference properties of simple gas hydrates has been proposed. The guest molecules affect interaction between adjacent water molecules distorting the hydrate lattice, which requires diverse values of reference properties for different gas hydrates. We performed simulations to validate the experimental data for determining Δ0, the chemical potential difference between water and theoretical empty cavity at the reference state, for structure II type gas hydrates. Simulations have also been used to observe the variation of the hydrate unit cell volume with temperature. All simulations were performed using TIP4P water molecules at the reference temperature and pressure conditions. The values were close to the experimental values obtained by the Lee-Holder model, considering lattice distortion.

  20. Dynamic determination reserves of the underground gas storage

    Institute of Scientific and Technical Information of China (English)

    谭羽非

    2004-01-01

    One of the key problems in the use of underground gas storage is frequent leakage. It can lead to the actual gas storage amount being less than that accounted for. Combining numerical simulation and parameter auto fit, this paper ascertains the dynamic variation of the pressure in the storage reservoir, adjusts the actual injecting and producing gas to fit the accounted pressure with the tested pressure, obtains the gas leakage of the storage, and then determines the difference between accounted amount and leakage amount. The result is the actual reserves of the storage. The simulation result shows that the method presented can provide a theoretic foundation for estimating the leakage amount, thereby ensuring the actual reserves, searching the leakage route,and reducing leakage by adjusting the storage method.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates.

    Science.gov (United States)

    Irigoyen, Joseba; Politakos, Nikolaos; Diamanti, Eleftheria; Rojas, Elena; Marradi, Marco; Ledezma, Raquel; Arizmendi, Layza; Rodríguez, J Alberto; Ziolo, Ronald F; Moya, Sergio E

    2015-01-01

    A novel and facile method was developed to produce hybrid graphene oxide (GO)-polyelectrolyte (PE) capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH) and polystyrenesulfonate sodium salt (PSS). Capsules where characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS) and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies.

  6. Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates

    Directory of Open Access Journals (Sweden)

    Joseba Irigoyen

    2015-12-01

    Full Text Available A novel and facile method was developed to produce hybrid graphene oxide (GO–polyelectrolyte (PE capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH and polystyrenesulfonate sodium salt (PSS. Capsules where characterized by transmission electron microscopy (TEM, atomic force microscopy (AFM, dynamic light scattering (DLS and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies.

  7. Empirical determinants of measles metapopulation dynamics in England and Wales.

    OpenAIRE

    Finkenstädt, B; Grenfell, B.

    1998-01-01

    A key issue in metapopulation dynamics is the relative impact of internal patch dynamics and coupling between patches. This problem can be addressed by analysing large spatiotemporal data sets, recording the local and global dynamics of metapopulations. In this paper, we analyse the dynamics of measles meta-populations in a large spatiotemporal case notification data set, collected during the pre-vaccination era in England and Wales. Specifically, we use generalized linear statistical models ...

  8. Dynamic characteristics of rocks and method of their determine

    Directory of Open Access Journals (Sweden)

    Radoslav Schügerl

    2009-01-01

    Full Text Available This paper presents selected problems of the research of the influence of technical vibrations on rocks. The vibrations are the products of the technological procedure, such as mining blasting, ramming of the piles, using of the drilling-equipment or vibration machines. The vibrations could be also evocated by road or train traffic. The most important dynamic characteristics of rocks are dynamic modulus of elasticity Edyn; dynamic modulus of deformation Edef, dyn; dynamic shear-modulus Gdyn; and especially dynamic Poisson´s ratio νdyn. These parameters were obtained by laboratory testing of conglomerate samples.

  9. Effects of a polyelectrolyte additive on the selective dialysis membrane permeability for low-molecular-weight proteins.

    Science.gov (United States)

    Krieter, Detlef H; Morgenroth, Andreas; Barasinski, Artur; Lemke, Horst-Dieter; Schuster, Oliver; von Harten, Bodo; Wanner, Christoph

    2007-02-01

    Improving the sieving characteristics of dialysis membranes enhances the clearance of low-molecular-weight (LMW) proteins and may have an impact on outcome in patients receiving haemodialysis. To approach this goal, a novel polyelectrolyte additive process was applied to a polyethersulphone (PES) membrane. Polyelectrolyte-modified PES was characterized in vitro by measuring complement activation and sieving coefficients of cytochrome c and serum albumin. In a prospective, randomized, cross-over study, instantaneous plasma water clearances and reduction rates of LMW proteins [beta(2)-microglobulin (b2m), cystatin c, myoglobin, retinol binding protein] were determined in eight patients receiving dialysis treatment with PES in comparison with polysulphone (PSU). Biocompatibility was assessed by determination of transient leucopenia, plasma levels of complement C5a, thrombin-antithrombin III (TAT), myeloperoxidase (MPO) and elastase (ELT). PES showed a steeper sieving profile and lower complement activation in vitro compared with PSU. Instantaneous clearance (69 +/- 8 vs. 58 +/- 3 ml/min; P dialysis). MPO, ELT and TAT did not differ between the two membranes. In contrast, leucopenia was less pronounced and C5a generation was significantly lower during dialysis with PES. Polyelectrolyte modification of PES results in a higher LMW protein removal and in optimized biocompatibility. Whether these findings translate into better outcome of patients receiving haemodialysis requires further studies.

  10. 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

  11. 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).

  12. 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...

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. Implementation of non-uniform FFT based Ewald summation in Dissipative Particle Dynamic method

    CERN Document Server

    Wang, Yong-Lei; Lu, Zhong-Yuan; 10.1016/j.jcp.2012.09.023

    2013-01-01

    The ENUF method, i.e., Ewald summation based on the Non-Uniform FFT technique (NFFT), is implemented in Dissipative Particle Dynamics (DPD) simulation scheme to fast and accurately calculate the electrostatic interactions at mesoscopic level. In a simple model electrolyte system, the suitable ENUF-DPD parameters, including the convergence parameter $\\alpha$, the NFFT approximation parameter $p$, and the cut-offs for real and reciprocal space contributions, are carefully determined. With these optimized parameters, the ENUF-DPD method shows excellent efficiency and scales as $\\mathcal{O}(N\\log N)$. The ENUF-DPD method is further validated by investigating the effects of charge fraction of polyelectrolyte, ionic strength and counterion valency of added salts on polyelectrolyte conformations. The simulations in this paper, together with a separately published work of dendrimer-membrane complexes, show that the ENUF-DPD method is very robust and can be used to study charged complex systems at mesoscopic level.

  2. 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.

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

    Science.gov (United States)

    Nejati Moshtaghin, Mahboubeh

    of FA, oppositely charged amphiphiles (surfactant-polyelectrolyte), and the charge ratio of the surfactant-polyelectrolyte on the extent of coacervation have been investigated. Furthermore, the chemical composition of each phase formed in the coacervate system was determined as a function of HFIP percentage. Phase diagrams of HFIP-PMA-CTAB and 2-propanol-PMA-CTAB were studied. The phase separation occurs over a wide range of polyelectrolyte, surfactant and alcohol concentration. In addition, a study of the dependence of coacervate volume on phase composition in different system (as defined by concentrations and mole charge ratio of amphihiles and alcohols) provided useful insight about possible underlying interactions and mechanisms. It has been concluded that neutralization favors coacervation in both systems. However, according to the compositional analysis of both HFIP and 2-propanol SPCC system, it seems that coacervation mechanisms are different. In Chapter III the properties of 2-propanol--SPCC, with analogous surfactant (CTAB) and polyelectrolyte (PMA) used in Chapter II, will be investigated. In particular, we are interested in examining the difference between the phase separation characteristics of the coacervates induced by 2-propanol and HFIP as coacervator. For this purpose, the phase behavior and the chemical composition of the phases will be analyzed as a function of 2-propanol and constituents concentrations. Chapter IV contains results of our investigations on the activity of a model enzyme (Trypsin) in 2-propanol- and FA-induced SPCC system. These investigations will facilitate understanding whether the aliphatic alcohol, AA- and FA-induced SPCC system denature the model enzymes. Such investigations also help in evaluation of the applicability of the coacervate systems developed in this work in proteomics where the proteolytic activity of enzymes is used for protein digestion. Finally, in Chapter V, the efficiency of the coacervate system (2-propanol

  4. A novel, biodegradable and reversible polyelectrolyte platform for topical-colonic delivery of pentosan polysulphate.

    Science.gov (United States)

    Shah, Hardik K; Conkie, Jim A; Tait, Robert C; Johnson, James R; Wilson, Clive G

    2011-02-14

    The goal of the present work was to develop a swellable hydrogel colonic delivery system, which would maximise the availability of the therapeutic agent at a site of inflammation, especially where the water is scarce. A novel method was developed to manufacture a biodegradable and reversible polyelectrolyte complex (PEC) containing chitosan and poly acrylic-acid (PAA). The PEC was analysed using FTIR and DSC, which confirmed the formation of non-permanent swollen gel-network at an alkaline pH. Pentosan polysulphate (PPS) was incorporated in a PEC and an activated partial thromboplastin time assay was developed to measure the release of PPS from PEC. In vitro studies suggested that the release of PPS was dependent on the initial drug loading and the composition of the PEC. The gel strength of the swollen network, determined using a texture analyser, was dependent on polymer composition and the amount of PPS incorporated. Bacterial enzymes were collected from the rat caecum and colon for the digestion studies and characterised for glucosidase activity, glucuronidase activity and protein content. The digestion of the reversible polyelectrolyte complexes was measured using a dinitro salicylic acid assay and an increased release of drug was also confirmed in the presence of bacterial enzymes.

  5. Polyelectrolyte carbon quantum-dots: new player as a noninvasive imaging probe in Drosophila.

    Science.gov (United States)

    Parvin, Nragish; Mandal, Tapas K; Roy, Partha

    2013-10-01

    It is since long that X-ray or magnetic resonance imaging is being used for biomedical diagnosis. But till date noninvasive soft tissue imaging is not very well established. Towards this end the dietary uptake of polyelectrolyte carbon quantum dots (PECQDs) and their uses as a fluorescent probe is a new approach for imaging live specimens. In the present study we demonstrate that polyelectrolyte carbon quantum dots, which are nontoxic and have fluorescence properties can be used for in vivo imaging of internal organs. Carbon quantum dots surface were abound in polymer of free carboxyl groups making it water soluble. Our used PECQDs are less than equal to 50 nm sized and are capable to emit multi colour fluorescence. It is synthesized from waste plant materials like shaded leaves, unused shrubs, herbs etc. An exposure of 1 ppm level of soluble carbon quantum dots for 12 hours in drosophila permitted the fluorescence microscopy imaging of the different stages of their development and their non invasive internal organs without any remarkable toxic effects. Finally the fluorescent material was found to be excreted out of the animals. The current data suggests that visualization of internal organs with a fluorescent probe in live cells could help in determining the efficacy of therapeutic treatments directly without the need of any invasive procedures.

  6. 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.

  7. 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.

  8. Role of finite populations in determining evolutionary dynamics

    Science.gov (United States)

    Ray, Tane S.; Payne, Karl A.; Moseley, L. Leo

    2008-02-01

    The connection between the finite size of an evolving population and its dynamical behavior is examined through analytical and computational studies of a simple model of evolution. The infinite population limit of the model is shown to be governed by a special case of the quasispecies equations. A flat fitness landscape yields identical results for the dynamics of infinite and finite populations. On the other hand, a monotonically increasing fitness landscape shows “epochs” in the dynamics of finite populations that become more pronounced as the rate of mutation decreases. The details of the dynamics are profoundly different for any two simulation runs in that events arising from the stochastic noise in the pseudorandom number sequence are amplified. As the population size is increased or, equivalently, the mutation rate is increased, these epochs become smaller but do not entirely disappear.

  9. 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...

  10. Empirical determinants of measles metapopulation dynamics in England and Wales.

    Science.gov (United States)

    Finkenstädt, B; Grenfell, B

    1998-02-07

    A key issue in metapopulation dynamics is the relative impact of internal patch dynamics and coupling between patches. This problem can be addressed by analysing large spatiotemporal data sets, recording the local and global dynamics of metapopulations. In this paper, we analyse the dynamics of measles meta-populations in a large spatiotemporal case notification data set, collected during the pre-vaccination era in England and Wales. Specifically, we use generalized linear statistical models to quantify the relative importance of local influences (birth rate and population size) and regional coupling on local epidemic dynamics. Apart from the proportional effect of local population size on case totals, the models indicate patterns of local and regional dynamic influences which depend on the current state of epidemics. Birth rate and geographic coupling are not associated with the size of major epidemics. By contrast, minor epidemics--and especially the incidence of local extinction of infection--are influenced both by birth rate and geographical coupling. Birth rate at a lag of four years provides the best fit, reflecting the delayed recruitment of susceptibles to school cohorts. A hierarchical index of spatial coupling to large centres provides the best spatial model. The model also indicates that minor epidemics and extinction patterns are more strongly influenced by this regional effect than the local impact of birth rate.

  11. Swellable drug-polyelectrolyte matrices of drug-carboxymethylcellulose complexes. Characterization and delivery properties.

    Science.gov (United States)

    Rigo, María V Ramírez; Allemandi, Daniel A; Manzo, Ruben H

    2009-02-01

    This article reports the development and delivery properties of swellable drug-polyelectrolyte matrices prepared with complexes of the acid form of carboxymethylcellulose (HCMC). Drug-polyelelectrolyte complexes (HCMC-D) were obtained by neutralization of HCMC with two model basic drugs (atenolol and metoclopramide). Characterization through FT-infrared spectroscopy, power X-ray diffraction, and DSC indicates the ionic nature of the interaction between the carboxylic groups of HCMC and the basic group of D. Matrices prepared by compacting (HCMC-D) alone or in a mixture with sodium carboxymethylcellulose were subjected to measurements of solvent up-take, dynamics of swelling, and release kinetics. Delivery rate of mixed matrices is a function of its composition and may be widely modulated. They exhibited anomalous delivery kinetics with Korsmeyer exponent n in the range 0.67-0.87. Experimental results indicate that the erosion of the hydrogel layer is the main delivery process.

  12. Ratchet rectification effect on the translocation of a flexible polyelectrolyte chain.

    Science.gov (United States)

    Mondal, Debasish; Muthukumar, M

    2016-08-28

    We report a three dimensional Langevin dynamics simulation of a uniformly charged flexible polyelectrolyte chain, translocating through an asymmetric narrow channel with periodically varying cross sections under the influence of a periodic external electric field. When reflection symmetry of the channel is broken, a rectification effect is observed with a favored direction for the chain translocation. For a given volume of the channel unit and polymer length, the rectification occurs below a threshold frequency of the external periodic driving force. We have also observed that the extent of the rectification varies non-monotonically with increasing molecular weight and the strength of geometric asymmetry of the channel. Observed non-monotonicity of the rectification performance has been interpreted in terms of a competition between two effects arising from the channel asymmetry and change in conformational entropy. An analytical model is presented with predictions consistent with the simulation results.

  13. 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...

  14. Synthesis and characterization of chitosan-based polyelectrolyte complexes, doped by quantum dots

    Science.gov (United States)

    Abuzova, N. V.; Gerasimova, M. A.; Slabko, V. V.; Slyusareva, E. A.

    2015-12-01

    Doping of polymer particles by a fluorophores results in the sensitization within the visible spectral region becoming very promising materials for sensor applications. Colloids of biocompatible chitosan-based polyelectrolyte complexes (PECs) doped with quantum dots (QD) of CdTe and CdSe/ZnS (with sizes of 2.0-2.4 nm) were synthesized and characterized by scanning electron microscopy, dynamic light scattering, ζ-potential measurements, absorption and luminescence (including time-resolved) spectroscopy. The influence of ionic strength (0.02-1.5 M) on absorption and photoluminescence properties of encapsulated into PEC and unencapsulated quantum dots was investigated. The stability of the emission intensity of the encapsulated quantum dots has been shown to be strongly dependent on concentration of quantum dots.

  15. 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.

  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. 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.

  18. 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.

  19. Mesophase Separation and Probe Dynamics in Protein-Polyelectrolyte Coacervates

    Science.gov (United States)

    Kayitmazer, A. Basak; Bohidar, H. B.; Mattison, K. W.; Bose, A.; Russo, P. S.; Dubin, P. L.

    2007-03-01

    Protein-PE coacervates (PPC's) are self-assembling monophasic biomacromolecular fluids whose unique properties arise from transient heterogeneities. Among these properties are: high viscosity coupled with anomalously high protein diffusivity; rheological behavior intermediate between viscous solutions and gels; and little perturbation of protein native state. Despite their discovery 50 years ago, structure of coacervates is still poorly understood. Among the two models suggested for coacervate structure so far, we have verified the validity of one that proposes two states for protein in the coacervate. Cryo-TEM and static light scattering experiments on bovine serum albumin-poly(diallydimethylammonium chloride) coacervates have revealed heterogeneous scattering centers of several hundred nm, consistent with the presence of partially inter-connected dense domains surrounded by a large proportion of dilute domains, inferred from rheology. Fluorescence photobleaching recovery measurements of protein self-diffusion in coacervates have revealed temporal and spatial mesophasic heterogeneities over broad time and length scales; i.e. 50-700 nm and 0.5-30 sec.

  20. 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.

  1. 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.

  2. 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.

  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. 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.

  5. 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.

  6. 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.

  7. 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.

  8. New Dynamic Spin Rig Capabilities Used to Determine Rotating Blade Dynamics

    Science.gov (United States)

    Provenza, Andrew J.

    2004-01-01

    The Dynamic Spin Rig Facility at the NASA Glenn Research Center is used to determine the structural response of rotating engine components without the effects of aerodynamic loading. Recently, this rig's capabilities were enhanced through the replacement of grease-lubricated ball bearings with magnetic bearings. Magnetic bearings offer a number of advantages--the most important here being that they not only fully support the rotor system, but excite it as well. Three magnetic bearings support the rotor and provide five axes of controlled motion: an x- and y-axis translation at each of two radial bearings and a z-axis translation in the vertical or axial direction. Sinusoidal excitation (most commonly used) can be imparted on the rotor through the radial magnetic bearings in either a fixed or rotating frame of reference. This excitation is added directly to the magnetic bearing control output. Since the rotor is fully levitated, large translations and rotations of the rotor system can be achieved. Some of the capabilities of this excitation system were determined and reported. The accelerations obtained at the tip of a titanium flat plate test article versus the swept sine excitation sent to both radial bearings in phase and perpendicular to the plane containing the two blades are shown. Recent tests required the excitation of fundamental bending and torsional blade resonances at rotor speeds up to 10,000 rpm. Successful fixed synchronous rotation of the excitation signal provided the best detectable blade resonant vibrations at excitation frequencies up to 1100 Hz for the particular blades of interest. A noncontacting laser measurement system was used to collect blade-tip motions. From these data, the amplitude and frequency of the motion could be determined as well as the blade damping properties. Damping could be determined using two methods: (1) free decay and (2) curve fitting the vibration amplitude as a function of frequency in and around the resonance of

  9. 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.

  10. 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

  11. 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...

  12. 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

  13. Length Scale Dependence of the Dynamic Properties of Hyaluronic Acid Solutions in the Presence of Salt

    Energy Technology Data Exchange (ETDEWEB)

    Horkay, Ferenc; Falus, Peter; Hecht, Anne-Marie; Geissler, Erik (CNRS-UMR); (NIH); (ILL)

    2010-12-07

    In solutions of the charged semirigid biopolymer hyaluronic acid in salt-free conditions, the diffusion coefficient D{sub NSE} measured at high transfer momentum q by neutron spin echo is more than an order of magnitude smaller than that determined by dynamic light scattering, D{sub DLS}. This behavior contrasts with neutral polymer solutions. With increasing salt content, D{sub DLS} approaches D{sub NSE}, which is independent of ionic strength. Contrary to theoretical expectation, the ion-polymer coupling, which dominates the low q dynamics of polyelectrolyte solutions, already breaks down at distance scales greater than the Debye-Hueckel length.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Dynamics of epileptic phenomena determined from statistics of ictal transitions

    NARCIS (Netherlands)

    Suffczynski, P.; Silva, F.H.L. da; Parra, J.; Velis, D.N.; Bouwman, B.M.; Rijn, C.M. van; Hese, P. van; Boon, P.; Khosravani, H.; Derchansky, M.; Carlen, P.; Kalitzin, S.

    2006-01-01

    In this paper, we investigate the dynamical scenarios of transitions between normal and paroxysmal state in epilepsy. We assume that some epileptic neural network are bistable i.e., they feature two operational states, ictal and interictal that co-exist. The transitions between these two states may

  3. Brownian dynamics determine universality of charge transport in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Sangoro, Joshua R [ORNL; Iacob, Ciprian [University of Leipzig; Mierzwa, Michal [University of Silesia, Uniwersytecka, Katowice, Poland; Paluch, Marian [University of Silesia, Uniwersytecka, Katowice, Poland; Kremer, Friedrich [University of Leipzig

    2012-01-01

    Broadband dielectric spectroscopy is employed to investigate charge transport in a variety of glass-forming ionic liquids over wide frequency, temperature and pressure ranges. Using a combination of Einstein, Einstein-Smoluchowski, and Langevin relations, the observed universal scaling of charge transport in ionic liquids is traced back to the dominant role of Brownian dynamics.

  4. Determining Equilibrium Constants for Dimerization Reactions from Molecular Dynamics Simulations

    NARCIS (Netherlands)

    De Jong, Djurre H.; Schafer, Lars V.; De Vries, Alex H.; Marrink, Siewert J.; Berendsen, Herman J. C.; Grubmueller, Helmut

    2011-01-01

    With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices c

  5. The study of a fluorescent biosensor based on polyelectrolyte microcapsules with encapsulated glucose oxidase

    Science.gov (United States)

    Kazakova, L. I.; Sirota, N. P.; Sirota, T. V.; Shabarchina, L. I.

    2017-09-01

    A fluorescent biosensor is synthesized and described. The biosensor consists of polyelectrolyte microcapsules with glucose oxidase (GOx) entrapped in the cavities and an oxygen-sensitive fluorescent indicator Ru(dpp) immobilized in shells, where Ru(dpp) is tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride. The theoretical activity of the encapsulated GOx and the effect storage time and medium composition have on the stability of sensor microcapsules are determined from polarographic measurements. No change in the activity of the encapsulated enzyme and or its loss to the storage medium are detected over the test period. The dispersion medium (water or a phosphate buffer) are shown to have no effect on the activity of microcapsules with immobilized GOx. The described optical sensor could be used as an alternative to electrochemical sensors for in vitro determination of glucose in the clinically important range of concentrations (up to 10 mmol/L).

  6. Interaction between immobilized polyelectrolyte complex nanoparticles and human mesenchymal stromal cells

    Directory of Open Access Journals (Sweden)

    Woltmann B

    2014-05-01

    Full Text Available Beatrice Woltmann,1 Bernhard Torger,2,3 Martin Müller,2,3,* Ute Hempel1,*1Dresden University of Technology, Faculty of Medicine Carl Gustav Carus, Institute of Physiological Chemistry, Dresden, Germany; 2Leibniz Institute of Polymer Research Dresden, Department of Polyelectrolytes and Dispersions, Dresden, Germany; 3Dresden University of Technology, Department of Chemistry and Food Chemistry, Dresden, Germany*These authors contributed equally to this workBackground: Implant loosening or deficient osseointegration is a major problem in patients with systemic bone diseases (eg, osteoporosis. For this reason, the stimulation of the regional cell population by local and sustained drug delivery at the bone/implant interface to induce the formation of a mechanical stable bone is promising. The purpose of this study was to investigate the interaction of polymer-based nanoparticles with human bone marrow-derived cells, considering nanoparticles’ composition and surface net charge.Materials and methods: Polyelectrolyte complex nanoparticles (PECNPs composed of the polycations poly(ethyleneimine (PEI, poly(L-lysine (PLL, or (N,N-diethylaminoethyldextran (DEAE in combination with the polyanions dextran sulfate (DS or cellulose sulfate (CS were prepared. PECNPs’ physicochemical properties (size, net charge were characterized by dynamic light scattering and particle charge detector measurements. Biocompatibility was investigated using human mesenchymal stromal cells (hMSCs cultured on immobilized PECNP films (5–50 nmol·cm-2 by analysis for metabolic activity of hMSCs in dependence of PECNP surface concentration by MTS (3-[4,5-dimethylthiazol-2-yl]-5-[3-carboxymethoxyphenyl]-2-[4-sulfophenyl]-2H-tetrazolium, inner salt assay, as well as cell morphology (phase contrast microscopy.Results: PECNPs ranging between ~50 nm and 150 nm were prepared. By varying the ratio of polycations and polyanions, PECNPs with a slightly positive (PEC+NP or negative (PEC

  7. 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)

  8. Dynamic determinants of the uncontrolled manifold during human quiet stance

    Directory of Open Access Journals (Sweden)

    Yasuyuki Suzuki

    2016-12-01

    Full Text Available Human postural sway during stance arises from coordinated multi-joint movements. Thus, a sway trajectory represented by a time-varying postural vector in the multiple-joint-angle-space tends to be constrained to a low-dimensional subspace. It has been proposed that the subspace corresponds to a manifold defined by a kinematic constraint, such that the position of the center of mass (CoM of the whole body is constant in time, referred to as the kinematic uncontrolled manifold (kinematic-UCM. A control strategy related to this hypothesis (CoM-control-strategy claims that the central nervous system (CNS aims to keep the posture close to the kinematic-UCM using a continuous feedback controller, leading to sway patterns that mostly occur within the kinematic-UCM, where no corrective control is exerted. An alternative strategy proposed by the authors (intermittent control-strategy claims that the CNS stabilizes posture by intermittently suspending the active feedback controller, in such a way to allow the CNS to exploit a stable manifold of the saddle-type upright equilibrium in the state-space of the system, referred to as the dynamic-UCM, when the state point is on or near the manifold. Although the mathematical definitions of the kinematic- and dynamic-UCM are completely different, both UCMs play similar roles in the stabilization of multi-joint upright posture. The purpose of this study was to compare the dynamic performance of the two control strategies. In particular, we considered a double-inverted-pendulum-model of postural control, and analyzed the two UCMs defined above. We first showed that the geometric configurations of the two UCMs are almost identical. We then investigated whether the UCM-component of experimental sway could be considered as passive dynamics with no active control, and showed that such UCM-component mainly consists of high frequency oscillations above 1 Hz, corresponding to anti-phase coordination between the ankle and

  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. The F-Landscape: Dynamically Determining The Multiverse

    Science.gov (United States)

    Li, Tianjun; Maxin, James A.; Nanopoulos, Dimitri V.; Walker, Joel W.

    2012-09-01

    We evolve our Multiverse Blueprints to characterize our local neighborhood of the String Landscape and the Multiverse of plausible string, M- and F-theory vacua. Building upon the tripodal foundations of (i) the Flipped SU(5) Grand Unified Theory (GUT), (ii) extra TeV-Scale vector-like multiplets derived out of F-theory, and (iii) the dynamics of No-Scale supergravity, together dubbed No-Scale F-SU(5), we demonstrate the existence of a continuous family of solutions which might adeptly describe the dynamics of distinctive universes. This Multiverse landscape of F-SU(5) solutions, which we shall refer to as the F-Landscape, accommodates a subset of universes compatible with the presently known experimental uncertainties of our own universe. We show that by secondarily minimizing the minimum of the scalar Higgs potential of each solution within the F-Landscape, a continuous hypervolume of distinct minimum minimorum can be engineered which comprise a regional dominion of universes, with our own universe cast as the bellwether. We conjecture that an experimental signal at the LHC of the No-Scale F-SU(5) framework's applicability to our own universe might sensibly be extrapolated as corroborating evidence for the role of string, M- and F-theory as a master theory of the Multiverse, with No-Scale supergravity as a crucial and pervasive reinforcing structure.

  13. The F-Landscape: Dynamically Determining the Multiverse

    CERN Document Server

    Li, Tianjun; Nanopoulos, Dimitri V; Walker, Joel W

    2011-01-01

    We evolve our Multiverse Blueprints to characterize our local neighborhood of the String Landscape and the Multiverse of plausible string, M- and F-theory vacua. Building upon the tripodal foundations of i) the Flipped SU(5) Grand Unified Theory (GUT), ii) extra TeV-Scale vector-like multiplets derived out of F-theory, and iii) the dynamics of No-Scale Supergravity, together dubbed No-Scale F-SU(5), we demonstrate the existence of a continuous family of solutions which might adeptly describe the dynamics of distinctive universes. This Multiverse landscape of F-SU(5) solutions, which we shall refer to as the F-Landscape, accommodates a subset of universes compatible with the presently known experimental uncertainties of our own universe. We show that by secondarily minimizing the minimum of the scalar Higgs potential of each solution within the F-Landscape, a continuous hypervolume of distinct minimum minimorum can be engineered which comprise a regional dominion of universes, with our own universe cast as the...

  14. Determination of Scaling Parameter and Dynamical Resonances in Complex-Rotated Hamiltonian Ⅱ: Numerical Analysis

    Institute of Scientific and Technical Information of China (English)

    LIU Zong-Liang; ZHAO Fang; LI Shao-Hua; ZHAO Mei-Shan; CHEN Chang-Yong

    2008-01-01

    This paper is concerned with the determination of a unique scaling parameter in complex scaling analysis and with accurate calculation of dynamics resonances. In the preceding paper we have presented a theoretical analysis and provided a formalism for dynamical resonance calculations. In this paper we present accurate numerical results for two non-trivial dynamical processes, namely, models of diatomie molecular predissoeiation and of barrier potential scattering for resonances. The results presented in this paper confirm our theoretical analysis, remove a theoretical ambiguity on determination of the complex scaling parameter, and provide an improved understanding for dynamical resonance calculations in rigged Hilbert space.

  15. 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.)

  16. 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

  17. Emulsion-core and polyelectrolyte-shell nanocapsules: biocompatibility and neuroprotection against SH-SY5Y cells

    Energy Technology Data Exchange (ETDEWEB)

    Piotrowski, Marek, E-mail: ncpiotro@cyf-kr.edu.pl; Szczepanowicz, Krzysztof [Polish Academy of Sciences, Jerzy Haber Institute of Catalysis and Surface Chemistry (Poland); Jantas, Danuta; Leśkiewicz, Monika; Lasoń, Władysław [Polish Academy of Sciences, Institute of Pharmacology (Poland); Warszyński, Piotr [Polish Academy of Sciences, Jerzy Haber Institute of Catalysis and Surface Chemistry (Poland)

    2013-11-15

    The emulsion-core and polyelectrolyte-coated nanocapsules, designed as water-insoluble neuroprotective drug delivery system, were synthesized using layer-by-layer saturation method. The isopropyl myristate was used as oil phase and docusate sodium salt as emulsifier. For the polyelectrolyte shell preparation, synthetic polyelectrolytes, cationic (PDADMAC, PAH, and PLL) and anionic (PGA) were used. The particle size and zeta potential of nanocapsules were characterized by the dynamic light scattering. The average size of synthesized nanocapsules ranged from ∼80 to ∼100 nm. Zeta potential values ranged from less than approximately −30 mV for the polyanion layers to greater than approximately +30 mV for the polycation layers. Biocompatibilities of the synthesized nanocarriers were evaluated against SH-SY5Y human neuroblastoma cells using various biochemical assays. The results obtained show that synthesized nanocapsules coated with PLL and PGA were nontoxic to SH-SY5Y cells, and they were used as nanocarriers for model neuroprotective drug (a calpain inhibitor MDL 28170). The neuroprotective action of the encapsulated MDL 28170 against hydrogen peroxide-induced oxidative stress cytotoxicity was evaluated in the same cell line. The results showed that nanoencapsulated form of MDL 28170 were biocompatible and protected SH-SY5Y cells against the H{sub 2}O{sub 2} (0.5 mM/24 h)-induced damage in 20–40 times lower concentrations than those of the same drug added directly to the culture medium. These data suggest that the nanoscale carriers of neuroprotective drugs might serve as novel promising therapeutic agents for oxidative stress-related neurodegenerative processes.

  18. Accurate determination of heteroclinic orbits in chaotic dynamical systems

    Science.gov (United States)

    Li, Jizhou; Tomsovic, Steven

    2017-03-01

    Accurate calculation of heteroclinic and homoclinic orbits can be of significant importance in some classes of dynamical system problems. Yet for very strongly chaotic systems initial deviations from a true orbit will be magnified by a large exponential rate making direct computational methods fail quickly. In this paper, a method is developed that avoids direct calculation of the orbit by making use of the well-known stability property of the invariant unstable and stable manifolds. Under an area-preserving map, this property assures that any initial deviation from the stable (unstable) manifold collapses onto them under inverse (forward) iterations of the map. Using a set of judiciously chosen auxiliary points on the manifolds, long orbit segments can be calculated using the stable and unstable manifold intersections of the heteroclinic (homoclinic) tangle. Detailed calculations using the example of the kicked rotor are provided along with verification of the relation between action differences and certain areas bounded by the manifolds.

  19. Entering and exiting the protein-polyelectrolyte coacervate phase via nonmonotonic salt dependence of critical conditions.

    Science.gov (United States)

    Antonov, Margarita; Mazzawi, Malek; Dubin, Paul L

    2010-01-11

    Critical conditions for coacervation of poly(dimethyldiallylammonium chloride) (PDADMAC) with bovine serum albumin were determined as a function of ionic strength, pH, and protein/polyelectrolyte stoichiometry. The resultant phase boundaries, clearly defined with this narrow molecular weight distribution PDADMAC sample, showed nonmonotonic ionic strength dependence, with the pH-induced onset of coacervation (at pH(phi)) occurring most readily at 20 mM NaCl. The corresponding onset of soluble complex formation, pH(c), determined using high-precision turbidimetry sensitive to changes of less than 0.1% transmittance units, mirrored the ionic strength dependence of pH(phi). This nonmonotonic binding behavior is attributable to simultaneous screening of short-range attraction and long-range repulsion. The similarity of pH(c) and pH(phi) was explained by the effect of salt on protein binding, and consequently on the number of bound proteins relative to that required for charge neutralization of the complex, a requirement for phase separation. Expansion of the coacervation regime with chitosan, a polycation with charge spacing similar to that of PDADMAC, could be due to either the charge mobility or chain stiffness of the former. The pH(phi) versus I phase boundary for PDADMAC correctly predicted entrance into and egress from the coacervation region by addition of either salt or water. The ability to induce or suppress coacervation via protein/polyelectrolyte stoichiometry r was found to be consistent with the proposed model. The results indicate that the conjoint effects of I, r, and pH on coacervation could be represented by a three-dimensional phase boundary.

  20. Core-Shell-Corona Silica Hybrid Nanoparticles Templated by Spherical Polyelectrolyte Brushes: A Study by Small Angle X-ray Scattering.

    Science.gov (United States)

    Han, Haoya; Li, Li; Wang, Weihua; Tian, Yuchuan; Wang, Yunwei; Wang, Junyou; von Klitzing, Regine; Guo, Xuhong

    2017-09-06

    Core-shell-corona silica/polymer hybrid nanoparticles with narrow size distribution were prepared in the template of spherical polyelectrolyte brushes (SPB) which consist of a solid polystyrene (PS) core densely grafted with linear poly(acrylic acid) (PAA) chains. The microstructure of obtained hybrid nanoparticles was studied by small-angle X-ray scattering (SAXS) and in combination with dynamic light scattering (DLS) and transmission electron microscopy (TEM). The generation of silica shell within the brush is confirmed by the significant increase of the electron density in the shell, and the silica shell showed a unique inner-loose-outer-dense structure, whose thickness is pH sensitive but is insensitive to ionic strength as revealed by fitting SAXS data. After dissolving the PS core, hollow silica nanoparticles were obtained and determined by SAXS, which should be ideal carriers for pH-triggered drug delivery. SAXS is confirmed to be a powerful method to characterize the core-shell-corona silica/polymer hybrid and hollow silica nanoparticles.

  1. Analysis and Report on SD2000: A Workshop to Determine Structural Dynamics Research for the Millenium

    Science.gov (United States)

    2007-11-02

    This ONR grant was to facilitate the meeting of an international group of researchers to examine the future of structural dynamics . A group of about...promptly dismissed it as an intellectual pursuit not useful in structural dynamics . In reflecting back over his career, he now views this as a mistake...smart materials, mechatronics, etc.) and determining the appropriate interaction between these new advances and structural dynamics was one of the

  2. Experimental determination of dynamic parameters of an industrial robot

    Science.gov (United States)

    Banas, W.; Cwikła, G.; Foit, K.; Gwiazda, A.; Monica, Z.; Sekala, A.

    2017-08-01

    In an industry increasingly used are industrial robots. Commonly used are two basic methods of programming, on-line programming and off-line programming. In both cases, the programming consists in getting to the selected points record this position, and set the order of movement of the robot, and the introduction of logical tests. Such a program is easy to write, and it is suitable for most industrial applications. Especially when the process is known, respectively slow and unchanging. In this case, the program is being prepared for a universal model of the robot with the appropriate geometry and are checked only collisions. Is not taken into account the dynamics of the robot and how it will really behave while in motion. For this reason, the robot programmed to be tested at a reduced speed, which is raised gradually to the final value. Depending on the complexity of the move and the proximity of the elements it takes a lot of time. It is easy to notice that the robot at different speeds have different trajectories and behaves differently.

  3. Determining tumor blood flow parameters from dynamic image measurements

    Science.gov (United States)

    Libertini, Jessica M.

    2008-11-01

    Many recent cancer treatments focus on preventing angiogenesis, the process by which a tumor promotes the growth of large and efficient capillary beds for the increased nourishment required to support the tumor's rapid growth[l]. To measure the efficacy of these treatments in a timely fashion, there is an interest in using data from dynamic sequences of contrast-enhanced medical imaging, such as MRI and CT, to measure blood flow parameters such as perfusion, permeability-surface-area product, and the relative volumes of the plasma and extracellular-extravascular space. Starting with a two compartment model presented by the radiology community[2], this work challenges the application of a simplification to this problem, which was originally developed to model capillary reuptake[3]. While the primary result of this work is the demonstration of the inaccuracy of this simplification, the remainder of the paper is dedicated to presenting alternative methods for calculating the perfusion and plasma volume coefficients. These methods are applied to model data sets based on real patient data, and preliminary results are presented.

  4. Determining tumor blood flow parameters from dynamic image measurements

    Energy Technology Data Exchange (ETDEWEB)

    Libertini, Jessica M [Division of Applied Mathematics, Brown University, Providence, Rhode Island 02906 (United States)], E-mail: Jessica_Libertini@brown.edu

    2008-11-01

    Many recent cancer treatments focus on preventing angiogenesis, the process by which a tumor promotes the growth of large and efficient capillary beds for the increased nourishment required to support the tumor's rapid growth. To measure the efficacy of these treatments in a timely fashion, there is an interest in using data from dynamic sequences of contrast-enhanced medical imaging, such as MRI and CT, to measure blood flow parameters such as perfusion, permeability-surface-area product, and the relative volumes of the plasma and extracellular-extravascular space. Starting with a two compartment model presented by the radiology community, this work challenges the application of a simplification to this problem, which was originally developed to model capillary reuptake. While the primary result of this work is the demonstration of the inaccuracy of this simplification, the remainder of the paper is dedicated to presenting alternative methods for calculating the perfusion and plasma volume coefficients. These methods are applied to model data sets based on real patient data, and preliminary results are presented.

  5. Experimental determination of the dynamics of an acoustically levitated sphere

    Energy Technology Data Exchange (ETDEWEB)

    Pérez, Nicolás, E-mail: nico@fisica.edu.uy [Centro Universitario de Paysandú, Universidad de la República, Paysandú (Uruguay); Andrade, Marco A. B. [Institute of Physics, University of São Paulo, São Paulo (Brazil); Canetti, Rafael [Facultad de Ingeniería, Universidad de la República, Montevideo (Uruguay); Adamowski, Julio C. [Department of Mechatronics and Mechanical Systems Engineering, Escola Politécnica, University of São Paulo, São Paulo (Brazil)

    2014-11-14

    Levitation of solids and liquids by ultrasonic standing waves is a promising technique to manipulate materials without contact. When a small particle is introduced in certain areas of a standing wave field, the acoustic radiation force pushes the particle to the pressure node. This movement is followed by oscillations of the levitated particle. Aiming to investigate the particle oscillations in acoustic levitation, this paper presents the experimental and numerical characterization of the dynamic behavior of a levitated sphere. To obtain the experimental response, a small sphere is lifted by the acoustic radiation force. After the sphere lift, it presents a damped oscillatory behavior, which is recorded by a high speed camera. To model this behavior, a mass-spring-damper system is proposed. In this model, the acoustic radiation force that acts on the sphere is theoretically predicted by the Gor'kov theory and the viscous forces are modeled by two damping terms, one term proportional to the square of the velocity and another term proportional to the particle velocity. The proposed model was experimentally verified by using different values of sound pressure amplitude. The comparison between numerical and experimental results shows that the model can accurately describe the oscillatory behavior of the sphere in an acoustic levitator.

  6. A dynamical phyllotaxis model to determine floral organ number.

    Directory of Open Access Journals (Sweden)

    Miho S Kitazawa

    2015-05-01

    Full Text Available How organisms determine particular organ numbers is a fundamental key to the development of precise body structures; however, the developmental mechanisms underlying organ-number determination are unclear. In many eudicot plants, the primordia of sepals and petals (the floral organs first arise sequentially at the edge of a circular, undifferentiated region called the floral meristem, and later transition into a concentric arrangement called a whorl, which includes four or five organs. The properties controlling the transition to whorls comprising particular numbers of organs is little explored. We propose a development-based model of floral organ-number determination, improving upon earlier models of plant phyllotaxis that assumed two developmental processes: the sequential initiation of primordia in the least crowded space around the meristem and the constant growth of the tip of the stem. By introducing mutual repulsion among primordia into the growth process, we numerically and analytically show that the whorled arrangement emerges spontaneously from the sequential initiation of primordia. Moreover, by allowing the strength of the inhibition exerted by each primordium to decrease as the primordium ages, we show that pentamerous whorls, in which the angular and radial positions of the primordia are consistent with those observed in sepal and petal primordia in Silene coeli-rosa, Caryophyllaceae, become the dominant arrangement. The organ number within the outmost whorl, corresponding to the sepals, takes a value of four or five in a much wider parameter space than that in which it takes a value of six or seven. These results suggest that mutual repulsion among primordia during growth and a temporal decrease in the strength of the inhibition during initiation are required for the development of the tetramerous and pentamerous whorls common in eudicots.

  7. Determination of the viscoelastic properties of elastomeric materials by the dynamic indentation method

    NARCIS (Netherlands)

    Vriend, Nathalie M.; Kren, Alexander P.

    2004-01-01

    In this paper the dynamic indentation test method, which is not often used, is discussed. The goal of the paper is to consider the possibility of applying a dynamic indentation test method to investigate rubber materials. The basic equations for the determination of the viscoelastic characteristics

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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

  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. 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. 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.

  19. CFD Based Determination of Dynamic Stability Derivatives in Yaw for a Bird

    Institute of Scientific and Technical Information of China (English)

    M. A. Moelyadi; G. Sachs

    2007-01-01

    Dynamic yaw stability derivatives of a gull bird are determined using Computational Fluid Dynamics(CFD) method. Two kinds of motions are applied for calculating the dynamic yaw stability derivatives CNr and CNβ. The first one relates to a lateral translation and, separately, to a yaw rotation. The second one consists of a combined translational and rotational motion. To determine dynamic yaw stability derivatives, the simulation of an unsteady flow with a bird model showing a harmonic motion is performed. The flow solution for each time step is obtained by solving unsteady Euler equations based on a finite volume approach for a small reduced frequency. Then, an evaluation of unsteady forces and moments for one cycle is conducted using harmonic Fourier analysis. The results of the dynamic yaw stability derivatives for both simulations of the model show a good agreement.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. In situ structure and dynamics of DNA origami determined through molecular dynamics simulations.

    Science.gov (United States)

    Yoo, Jejoong; Aksimentiev, Aleksei

    2013-12-10

    The DNA origami method permits folding of long single-stranded DNA into complex 3D structures with subnanometer precision. Transmission electron microscopy, atomic force microscopy, and recently cryo-EM tomography have been used to characterize the properties of such DNA origami objects, however their microscopic structures and dynamics have remained unknown. Here, we report the results of all-atom molecular dynamics simulations that characterized the structural and mechanical properties of DNA origami objects in unprecedented microscopic detail. When simulated in an aqueous environment, the structures of DNA origami objects depart from their idealized targets as a result of steric, electrostatic, and solvent-mediated forces. Whereas the global structural features of such relaxed conformations conform to the target designs, local deformations are abundant and vary in magnitude along the structures. In contrast to their free-solution conformation, the Holliday junctions in the DNA origami structures adopt a left-handed antiparallel conformation. We find the DNA origami structures undergo considerable temporal fluctuations on both local and global scales. Analysis of such structural fluctuations reveals the local mechanical properties of the DNA origami objects. The lattice type of the structures considerably affects global mechanical properties such as bending rigidity. Our study demonstrates the potential of all-atom molecular dynamics simulations to play a considerable role in future development of the DNA origami field by providing accurate, quantitative assessment of local and global structural and mechanical properties of DNA origami objects.

  5. 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.

  6. The determination of the attitude and attitude dynamics of TeamSat

    DEFF Research Database (Denmark)

    Betto, Maurizio; Jørgensen, John Leif; Riis, Troels

    1999-01-01

    , in space, multiple autonomous processes intended for spacecraft applications such as autonomous star identification, attitude determination and identification and tracking of non-stellar objects, imaging and real-time compression of image and science data for further ground analysis. AVS successfully...... determined the attitude and attitude dynamics of TeamSat....

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Evaluation of experimental methods for determining dynamic stiffness and damping of composite materials

    Science.gov (United States)

    Bert, C. W.; Clary, R. R.

    1974-01-01

    Various methods potentially usable for determining dynamic stiffness and damping of composite materials are reviewed. Of these, the following most widely used techniques are singled out for more detailed discussion: free vibration, pulse propagation, and forced vibration response. To illustrate the usefulness and validity of dynamic property data, their application in dynamic analyses and comparison with measured structural response are described for the following composite-material structures: free-free sandwich beam with glass-epoxy facings, clamped-edge sandwich plate with similar facings, free-end sandwich conical shell with similar facings, and boron-epoxy free plate with layers arranged at various orientations.

  13. Reinterpretation of Dynamic Vibrational Spectroscopy to Determine the Molecular Structure and Dynamics of Ferrocene.

    Science.gov (United States)

    Best, Stephen P; Wang, Feng; Islam, M Tauhidul; Islam, Shawkat; Appadoo, Dominique; Trevorah, Ryan M; Chantler, Christopher T

    2016-12-12

    Molecular distortion of dynamic molecules gives a clear signature in the vibrational spectra, which can be modeled to give estimates of the energy barrier and the sensitivity of the frequencies of the vibrational modes to the reaction coordinate. The reaction coordinate method (RCM) utilizes ab initio-calculated spectra of the molecule in its ground and transition states together with their relative energies to predict the temperature dependence of the vibrational spectra. DFT-calculated spectra of the eclipsed (D5h ) and staggered (D5d ) forms of ferrocene (Fc), and its deuterated analogue, within RCM explain the IR spectra of Fc in gas (350 K), solution (300 K), solid solution (7-300 K), and solid (7-300 K) states. In each case the D5h rotamer is lowest in energy but with the barrier to interconversion between rotamers higher for solution-phase samples (ca. 6 kJ mol(-1) ) than for the gas-phase species (1-3 kJ mol(-1) ). The generality of the approach is demonstrated with application to tricarbonyl(η(4) -norbornadiene)iron(0), Fe(NBD)(CO)3 . The temperature-dependent coalescence of the ν(CO) bands of Fe(NBD)(CO)3 is well explained by the RCM without recourse to NMR-like rapid exchange. The RCM establishes a clear link between the calculated ground and transition states of dynamic molecules and the temperature-dependence of their vibrational spectra. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 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.

  15. 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.

  16. 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.

  17. Preparation, characterization and application of polyelectrolytes/TiO{sub 2}/CdSe self-assembled films

    Energy Technology Data Exchange (ETDEWEB)

    Faria, Ana Claudia R. [Centro de Ciências Exatas e Tecnologia, Universidade de Caxias do Sul – UCS, Rua Francisco Getúlio Vargas, 1130, Caxias do Sul 95070-560, RS (Brazil); Menezes, Frederico D.; Milani, Raquel [Universidade Federal de Pernambuco – UFPE, Av. Prof. Moraes Rego, 1235, Recife 50740-560, PE (Brazil); Pereira, Marcelo B.; Gonçalves, Renato V.; Horowitz, Flavio [Instituto de Física, Universidade Federal do Rio Grande do Sul – UFRGS, Av. Bento Gonçalves, 9500, Porto Alegre 91501-970, RS (Brazil); Giovanela, Marcelo [Centro de Ciências Exatas e Tecnologia, Universidade de Caxias do Sul – UCS, Rua Francisco Getúlio Vargas, 1130, Caxias do Sul 95070-560, RS (Brazil); Machado, Giovanna [Universidade Federal de Pernambuco – UFPE, Av. Prof. Moraes Rego, 1235, Recife 50740-560, PE (Brazil); Centro de Tecnologias Estratégicas do Nordeste – CETENE, Av. Prof. Luiz Freire, 01, Recife 50740-540, PE (Brazil); Crespo, Janaina S., E-mail: jscrespo@ucs.br [Centro de Ciências Exatas e Tecnologia, Universidade de Caxias do Sul – UCS, Rua Francisco Getúlio Vargas, 1130, Caxias do Sul 95070-560, RS (Brazil)

    2014-01-31

    The aim of this work was to prepare self-assembled films (SAF) via a layer-by-layer technique and to characterize the films by applying several instrumental techniques. The cationic system was composed of the organic polyelectrolyte poly(diallyldimethylammonium chloride) and the inorganic semiconductor cadmium selenide (CdSe), whereas the anionic system was composed of poly(acrylic acid) and nanoparticles of the photoactive semiconductor titanium dioxide (TiO{sub 2}). Through measurements of the diffuse reflectance spectrum, absorption bands were observed in the near ultraviolet region for TiO{sub 2} and in the visible region for CdSe. The thicknesses of the SAF were determined through profilometry and scanning electron microscopy techniques, and the obtained values were on the order of microns. Finally, the SAF were irradiated with a Xe/Hg lamp, and the results indicated their potential for solar hydrogen production. - Highlights: • Development of polyelectrolytes/TiO{sub 2}/CdSe self-assembled films • Films characterization applying several instrumental techniques • Potential application in the solar hydrogen production.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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)

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. The application of virtual prototyping methods to determine the dynamic parameters of mobile robot

    Science.gov (United States)

    Kurc, Krzysztof; Szybicki, Dariusz; Burghardt, Andrzej; Muszyńska, Magdalena

    2016-04-01

    The paper presents methods used to determine the parameters necessary to build a mathematical model of an underwater robot with a crawler drive. The parameters present in the dynamics equation will be determined by means of advanced mechatronic design tools, including: CAD/CAE software andMES modules. The virtual prototyping process is described as well as the various possible uses (design adaptability) depending on the optional accessories added to the vehicle. A mathematical model is presented to show the kinematics and dynamics of the underwater crawler robot, essential for the design stage.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Single-molecule elasticity of single-stranded DNA, a model flexible polyelectrolyte

    Science.gov (United States)

    McIntosh, Dustin B.

    Understanding the structure of unfolded, flexible polyelectrolytes is important for our comprehension of basic processes in molecular biology (e.g., RNA and protein folding) and our ability to exploit the polymers in technology (e.g., in self-assembled nanostructures). Here, we investigate the structure of single single-stranded DNA molecules and their interactions with ions using magnetic tweezers. Our data reveal that single-stranded DNA is not well-described by ideal polymer models such as the Worm-Like Chain. At low force, we report the first experimental observation of a nonlinear elastic regime revealing the relevance of long-range excluded volume effects. At high force, the extension scales as a logarithm in monovalent salt. Molecular dynamics simulations indicate that this logarithmic regime is the result of ion-stabilized wrinkles at short-length scales along the polymer backbone. Addition of divalent salt to the buffer results in enhanced elasticity indicating increased wrinkling or polymer ''wrapping" around the divalent ions. Using a thermodynamic identity, we are able to count ions as they are released into the bulk upon polymer elongation. We find that ssDNA releases significantly more ions than dsDNA. We posit that the recently termed ''Snake-Like Chain" model (Ullner, J. Phys. Chem B (2003)) for flexible polyelectrolytes may explain these observations. As a first step towards characterizing biologically relevant nucleic acid structures, we measure the effects of base-stacking on ssDNA elasticity. We find that base-stacking in poly(dA) significantly enhances the rigidity of the polymer as evidenced by the low-force elasticity. The unstacking transition of poly(dA) at high force reveals that the intrinsic electrostatic tension on the molecule varies significantly more weakly on salt concentration than predictions from mean-field models. Further, we provide a model-independent estimate of the free energy difference between stacked and unstacked nucleic

  15. Determination of metal ions by fluorescence anisotropy exhibits a broad dynamic range

    Science.gov (United States)

    Thompson, Richard B.; Maliwal, Badri P.; Fierke, Carol A.

    1998-05-01

    Recently, we have shown that metal ions free in solution may be determined at low levels by fluorescence anisotropy (polarization) measurements. Anisotropy measurements enjoy the advantages of wavelength ratiometric techniques for determining metal ions such as calcium, because anisotropy measurements are ratiometric as well. Furthermore, fluorescence anisotropy may be imaged in the microscope. An advantage of anisotropy not demonstrated for wavelength ratiometric approaches using indicators such as Fura-2 and Indo-1 is that under favorable circumstances anisotropy-based determinations exhibit a much broader dynamic range in metal ion concentration. Determinations of free Zn(II) in the picomolar range are demonstrated.

  16. Computational fluid dynamics vs. inverse dynamics methods to determine passive drag in two breaststroke glide positions.

    Science.gov (United States)

    Costa, L; Mantha, V R; Silva, A J; Fernandes, R J; Marinho, D A; Vilas-Boas, J P; Machado, L; Rouboa, A

    2015-07-16

    Computational fluid dynamics (CFD) plays an important role to quantify, understand and "observe" the water movements around the human body and its effects on drag (D). We aimed to investigate the flow effects around the swimmer and to compare the drag and drag coefficient (CD) values obtained from experiments (using cable velocimetry in a swimming pool) with those of CFD simulations for the two ventral gliding positions assumed during the breaststroke underwater cycle (with shoulders flexed and upper limbs extended above the head-GP1; with shoulders in neutral position and upper limbs extended along the trunk-GP2). Six well-trained breaststroke male swimmers (with reasonable homogeneity of body characteristics) participated in the experimental tests; afterwards a 3D swimmer model was created to fit within the limits of the sample body size profile. The standard k-ε turbulent model was used to simulate the fluid flow around the swimmer model. Velocity ranged from 1.30 to 1.70 m/s for GP1 and 1.10 to 1.50 m/s for GP2. Values found for GP1 and GP2 were lower for CFD than experimental ones. Nevertheless, both CFD and experimental drag/drag coefficient values displayed a tendency to jointly increase/decrease with velocity, except for GP2 CD where CFD and experimental values display opposite tendencies. Results suggest that CFD values obtained by single model approaches should be considered with caution due to small body shape and dimension differences to real swimmers. For better accuracy of CFD studies, realistic individual 3D models of swimmers are required, and specific kinematics respected.

  17. The six determinants of gait and the inverted pendulum analogy: A dynamic walking perspective.

    Science.gov (United States)

    Kuo, Arthur D

    2007-08-01

    We examine two prevailing, yet surprisingly contradictory, theories of human walking. The six determinants of gait are kinematic features of gait proposed to minimize the energetic cost of locomotion by reducing the vertical displacement of the body center of mass (COM). The inverted pendulum analogy proposes that it is beneficial for the stance leg to behave like a pendulum, prescribing a more circular arc, rather than a horizontal path, for the COM. Recent literature presents evidence against the six determinants theory, and a simple mathematical analysis shows that a flattened COM trajectory in fact increases muscle work and force requirements. A similar analysis shows that the inverted pendulum fares better, but paradoxically predicts no work or force requirements. The paradox may be resolved through the dynamic walking approach, which refers to periodic gaits produced almost entirely by the dynamics of the limbs alone. Demonstrations include passive dynamic walking machines that descend a gentle slope, and active dynamic walking robots that walk on level ground. Dynamic walking takes advantage of the inverted pendulum mechanism, but requires mechanical work to transition from one pendular stance leg to the next. We show how the step-to-step transition is an unavoidable energetic consequence of the inverted pendulum gait, and gives rise to predictions that are experimentally testable on humans and machines. The dynamic walking approach provides a new perspective, focusing on mechanical work rather than the kinematics or forces of gait. It is helpful for explaining human gait features in a constructive rather than interpretive manner.

  18. 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.

  19. LOSS FACTOR AND DYNAMIC YOUNG MODULUS DETERMINATION FOR COMPOSITE SANDWICH BARS REINFORCED WITH STEEL FABRIC

    Directory of Open Access Journals (Sweden)

    Cosmin-Mihai MIRIŢOIU

    2015-05-01

    Full Text Available In this paper I have build some composite sandwich bars. For these bars I have determined the dynamic response by recording their free vibrations. These bars have the core made of polypropylene honeycomb with upper and lower layers reinforced with steel wire mesh. For these bars I have determined the the eigenfrequency of the first eigenmode in this way: the bar was embedded at one end and free at the other where there was placed an accelerometer at 10 mm distance from the edge and I applied an initial force at the free end. I have determined the eigenfrequency because I will use its values for the loss factor and dynamic Young modulus determination.

  20. 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.

  1. 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.

  2. A Unified Approach to Nonlinear Dynamic Inversion Control with Parameter Determination by Eigenvalue Assignment

    Directory of Open Access Journals (Sweden)

    Yu-Chi Wang

    2015-01-01

    Full Text Available This paper presents a unified approach to nonlinear dynamic inversion control algorithm with the parameters for desired dynamics determined by using an eigenvalue assignment method, which may be applied in a very straightforward and convenient way. By using this method, it is not necessary to transform the nonlinear equations into linear equations by feedback linearization before beginning control designs. The applications of this method are not limited to affine nonlinear control systems or limited to minimum phase problems if the eigenvalues of error dynamics are carefully assigned so that the desired dynamics is stable. The control design by using this method is shown to be robust to modeling uncertainties. To validate the theory, the design of a UAV control system is presented as an example. Numerical simulations show the performance of the design to be quite remarkable.

  3. Sex ratio selection and multi-factorial sex determination in the housefly : A dynamic model

    NARCIS (Netherlands)

    Kozielska, M.A.; Pen, I.R.; Beukeboom, L.W.; Weissing, F.J.

    Sex determining (SD) mechanisms are highly variable between different taxonomic groups and appear to change relatively quickly during evolution. Sex ratio selection could be a dominant force causing such changes. We investigate theoretically the effect of sex ratio selection on the dynamics of a

  4. Determination of thermal inactivation kinetics of Listeria monocytogenes in chicken meat by isothermal and dynamic methods

    Science.gov (United States)

    The objective of this research is to determine the thermal inactivation kinetics of Listeria monocytogenes in chicken breast meat using both isothermal and dynamic conditions. A four-strain cocktail of L. monocytogenes was inoculated to chicken breast meat. Isothermal studies were performed by sub...

  5. Error compensation of single-antenna attitude determination using GNSS for Low-dynamic applications

    Science.gov (United States)

    Chen, Wen; Yu, Chao; Cai, Miaomiao

    2017-04-01

    GNSS-based single-antenna pseudo-attitude determination method has attracted more and more attention from the field of high-dynamic navigation due to its low cost, low system complexity, and no temporal accumulated errors. Related researches indicate that this method can be an important complement or even an alternative to the traditional sensors for general accuracy requirement (such as small UAV navigation). The application of single-antenna attitude determining method to low-dynamic carrier has just started. Different from the traditional multi-antenna attitude measurement technique, the pseudo-attitude attitude determination method calculates the rotation angle of the carrier trajectory relative to the earth. Thus it inevitably contains some deviations comparing with the real attitude angle. In low-dynamic application, these deviations are particularly noticeable, which may not be ignored. The causes of the deviations can be roughly classified into three categories, including the measurement error, the offset error, and the lateral error. Empirical correction strategies for the formal two errors have been promoted in previous study, but lack of theoretical support. In this paper, we will provide quantitative description of the three type of errors and discuss the related error compensation methods. Vehicle and shipborne experiments were carried out to verify the feasibility of the proposed correction methods. Keywords: Error compensation; Single-antenna; GNSS; Attitude determination; Low-dynamic

  6. Pulsatile microfluidics as an analytical tool for determining the dynamic characteristics of microfluidic systems

    DEFF Research Database (Denmark)

    Vedel, Søren; Olesen, Laurits Højgaard; Bruus, Henrik

    2010-01-01

    -filled interconnected elastic microfluidic tubes containing a large, trapped air bubble and driven by a pulsatile pressure difference. We demonstrate good agreement between the system-level model and the experimental results, allowing us to determine the dynamic time scales of the system. However, the generic analysis...

  7. Sex ratio selection and multi-factorial sex determination in the housefly : A dynamic model

    NARCIS (Netherlands)

    Kozielska, M.A.; Pen, I.R.; Beukeboom, L.W.; Weissing, F.J.

    2006-01-01

    Sex determining (SD) mechanisms are highly variable between different taxonomic groups and appear to change relatively quickly during evolution. Sex ratio selection could be a dominant force causing such changes. We investigate theoretically the effect of sex ratio selection on the dynamics of a mul

  8. Determination of the smoke-plume heights and their dynamics with ground-based scanning LIDAR

    Science.gov (United States)

    V. Kovalev; A. Petkov; C. Wold; S. Urbanski; W. M. Hao

    2015-01-01

    Lidar-data processing techniques are analyzed, which allow determining smoke-plume heights and their dynamics and can be helpful for the improvement of smoke dispersion and air quality models. The data processing algorithms considered in the paper are based on the analysis of two alternative characteristics related to the smoke dispersion process: the regularized...

  9. Upper Limb Asymmetries in the Perception of Proprioceptively Determined Dynamic Position Sense

    Science.gov (United States)

    Goble, Daniel J.; Brown, Susan H.

    2010-01-01

    Recent studies of position-related proprioceptive sense have provided evidence of a nonpreferred left arm advantage in right-handed individuals. The present study sought to determine whether similar asymmetries might exist in "dynamic position" sense. Thirteen healthy, right-handed adults were blindfolded and seated with arms placed on…

  10. Thickness determination in textile material design: dynamic modeling and numerical algorithms

    Science.gov (United States)

    Xu, Dinghua; Ge, Meibao

    2012-03-01

    Textile material design is of paramount importance in the study of functional clothing design. It is therefore important to determine the dynamic heat and moisture transfer characteristics in the human body-clothing-environment system, which directly determine the heat-moisture comfort level of the human body. Based on a model of dynamic heat and moisture transfer with condensation in porous fabric at low temperature, this paper presents a new inverse problem of textile thickness determination (IPTTD). Adopting the idea of the least-squares method, we formulate the IPTTD into a function minimization problem. By means of the finite-difference method, quasi-solution method and direct search method for one-dimensional minimization problems, we construct iterative algorithms of the approximated solution for the IPTTD. Numerical simulation results validate the formulation of the IPTTD and demonstrate the effectiveness of the proposed numerical algorithms.

  11. Testing Object-Oriented Programs using Dynamic Aspects and Non-Determinism

    DEFF Research Database (Denmark)

    Achenbach, Michael; Ostermann, Klaus

    2010-01-01

    without parameterization or generation of tests. It also eases modelling naturally non-deterministic program features like IO or multi-threading in integration tests. Dynamic AOP facilitates powerful design adaptations without exposing test features, keeping the scope of these adaptations local to each...... test. We also combine non-determinism and dynamic aspects in a new approach to testing multi-threaded programs using co-routines.......The implementation of unit tests with mock objects and stubs often involves substantial manual work. Stubbed methods return simple default values, therefore variations of these values require separate test cases. The integration of mock objects often requires more infrastructure code and design...

  12. Determination of Mean Inner Potential by Electron Holography Along with Electron Dynamic Simulation

    Institute of Scientific and Technical Information of China (English)

    王岩国; 刘红荣; 杨奇斌; 张泽

    2003-01-01

    Off-axis electron holography in a field-emission-gun transmission electron microscope and electron dynamic simulation is used to determine the mean inner potential of copper. The phase shift of object wave versus specimen thickness is calculated up to 30 nm using electron dynamic formula, and the sample thickness is decided by match of the experimental and calculated phase shift. Based on the measured phase shift, the calculated mean inner potential of Cu is 21.2 V, which agrees with the reported values within the experimental error.

  13. 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)

  14. Experimental determination of dynamic characteristics of the VentrAssist implantable rotary blood pump.

    Science.gov (United States)

    Chung, Michael K H; Zhang, Nong; Tansley, Geoff D; Qian, Yi

    2004-12-01

    The VentrAssist implantable rotary blood pump, intended for long-term ventricular assist, is under development and is currently being tested for its rotor-dynamic stability. The pump consists of a shaftless impeller, which also acts as the rotor of the brushless DC motor. The impeller remains passively suspended in the pump cavity by hydrodynamic forces, which result from the small clearances between the outside surfaces of the impeller and the pump cavity. These small clearances range from approximately 50 microm to 230 microm in size in the version of pump reported here. This article presents experimental investigation into the dynamic characteristics of the impeller-bearing-pump housing system of the rotary blood pump for increasing pump speeds at different flow rates. The pump was mounted on a suspension system consisting of a platform and springs, where the natural frequency and damping ratio for the suspension system were determined. Real-time measurements of the impeller's displacement were performed using Hall effect sensors. A vertical disturbance force was exerted onto the pump housing, causing the impeller to be displaced in vertical direction from its dynamic equilibrium position within the pump cavity. The impeller displacement was represented by a decaying sine wave, which indicated the impeller restoring to its equilibrium position. From the decaying sine wave the natural frequency and stiffness coefficient of the system were determined. Furthermore, the logarithmic decrement method was used to determine the damping ratio and eventually the damping coefficient of the system. Results indicate that stiffness and damping coefficients increased as flow rate and pump speed increased, representing an increase in stability with these changing conditions. However, pump speed had a greater influence on the stiffness and damping coefficients than flow rate did, which was evident through dynamic analysis. Overall the experimental method presented in this

  15. 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

  16. Dynamic capabilities for cooperation in Brazilian multinational and factors determining its management

    Directory of Open Access Journals (Sweden)

    Priscila Rezende da Costa

    2015-05-01

    Full Text Available In the context of emerging companies’ growth, current challenges depend on the local generation of product and process innovations, as well as dynamic capability to generate innovative solutions cooperatively and new globe business models. The objective of this study is to analyse the determining managerial factors for the dynamic capability of cooperation in Brazilian multinationals (BMNs. A survey was conducted with a sample of 60 BMNs, and a structured questionnaire and statistical tests with factorial analysis and Cronbach's alpha were used. The aggregate analysis of the results indicates that BMNs are going through a transitional process between the operational capability of cooperation and the capability for dynamic cooperation, which are relevant to the continuous adaptation of already-established cooperative management routines and the evaluation and incorporation of the relational capability of management practices that consider systemic flows, open innovation and integrate strategic intentionality into cooperative processes.

  17. Determination of dynamic performance of freight cars taking into account technical condition of side bearers

    Directory of Open Access Journals (Sweden)

    S.Myamlin

    2013-02-01

    Full Text Available Purpose. The railway transport plays an important role in social and economic life of the country and carries out the large containment of transportation activities. The transport industry should migrate towards innovation changes and increase its significance as an important transit subsystem on the way of renovation of both the infrastructure and the strategy of all transportation process components including the interaction with other transport modes. At present the life sets strategic challenges for the railway branch, and the basic goals among them are as follows: high-speed train traffic development, increase of the weight of freight trains, new rolling stock development etc. Due to the urgency of this subject, the researchers should cope with the task devoted to one of aspects of improving the freight transportation efficiency, namely to the study of effects of various factors and characteristics of technical conditions of the freight cars running gears (which are unavoidable to arise during operation on their basic dynamic indices. The deviations of technical conditions of running gears from the normal state of the wedge system of bogie swing suspension also play an important role among them. The purpose of the paper is to investigate the influence of different factors of the technical conditions of freight car running gears (size deviation in both the bearers and the wedge system during operation on their basic indices – coefficients of horizontal and vertical dynamics, vehicle body acceleration, frame strength, and derailment stability coefficient. Methodology. The study was conducted by numerical integration and mathematical modeling of the freight car dynamic loading using the software package “Dynamics of Rail Vehicles” (“DYNRAIL”. Findings. As a result of the research for freight car dynamic coefficients determination taking into account technical conditions of the side bearers, the dependencies of the basic freight cars

  18. Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald; Pleticha, F. Douglas; Hanley, Luke

    2011-03-14

    The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.

  19. 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.

  20. Surface Property and Stability of Transparent Superhydrophobic Coating Based on SiO2-Polyelectrolyte Multilayer

    Directory of Open Access Journals (Sweden)

    Sunisa JINDASUWAN

    2016-05-01

    Full Text Available Artificial superhydrophobic films were deposited onto a glass slide by performing layer-by-layer deposition of 3.5 bilayers of poly(allylamine hydrochloride/ poly(acrylic acid polyelectrolyte, followed by a layer of SiO2 nanoparticles of various amounts to enhance the surface roughness and a fluorosilane to reduce the surface free energy. Higher SiO2 content incorporated into the films resulted in rougher surface and higher water contact angle. The total surface free energy determined by using the Owens-Wendt equation dramatically decreased from 31.46 mJ·m-2 for the film having the relatively flat surface to only 1.16 mJ·m-2 for the film having the highest surface roughness of 60.2 ± 1.1 nm. All the films were optically transparent and had excellent adhesion based on the peel test. Indoor and accelerated weathering tests revealed good weathering stability.DOI: http://dx.doi.org/10.5755/j01.ms.22.2.12952

  1. Formation of redispersible polyelectrolyte complex nanoparticles from gallic acid-chitosan conjugate and gum arabic.

    Science.gov (United States)

    Hu, Qiaobin; Wang, Taoran; Zhou, Mingyong; Xue, Jingyi; Luo, Yangchao

    2016-11-01

    Polyelectrolyte complex (PEC) nanoparticles between chitosan (CS) and biomacromolecules offer better physicochemical properties as delivery vehicles for nutrients than other CS-based nanoparticles. Our major objective was to fabricate PEC nanoparticles between water soluble gallic acid-chitosan conjugate (GA-CS) and gum arabic. The optimal fabrication method, physicochemical characteristics and stability were investigated. Furthermore, we also evaluated the effects of nano spray drying technology on the morphology and redispersibility of nanoparticle powders using Buchi B-90 Nano Spray Dryer. Results showed that the mass ratio between GA-CS and gum arabic and the preparation pH had significant contributions in determining the particle size and count rate of the nanoparticles, with the ratio of 3:1 and pH 5.0 being the optimal conditions that resulted in 112.2nm and 122.9kcps. The polyethylene glycol (PEG) played a vital role in forming the well-separated spray dried nanoparticles. The most homogeneous nanoparticles with the smoothest surface were obtained when the mass ratio of GA-CS and PEG was 1:0.5. In addition, the GA-CS/gum arabic spray dried nanoparticles exhibited excellent water-redispersibiliy compared to native CS/gum arabic nanoparticles. Our results demonstrated GA-CS/gum arabic nanoparticles were successfully fabricated with promising physicochemical properties and great potential for their applications in food and pharmaceutical industries. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Surface Property and Stability of Transparent Superhydrophobic Coating Based on SiO2-Polyelectrolyte Multilayer

    Directory of Open Access Journals (Sweden)

    Sunisa JINDASUWAN

    2016-05-01

    Full Text Available Artificial superhydrophobic films were deposited onto a glass slide by performing layer-by-layer deposition of 3.5 bilayers of poly(allylamine hydrochloride/ poly(acrylic acid polyelectrolyte, followed by a layer of SiO2 nanoparticles of various amounts to enhance the surface roughness and a fluorosilane to reduce the surface free energy. Higher SiO2 content incorporated into the films resulted in rougher surface and higher water contact angle. The total surface free energy determined by using the Owens-Wendt equation dramatically decreased from 31.46 mJ·m-2 for the film having the relatively flat surface to only 1.16 mJ·m-2 for the film having the highest surface roughness of 60.2 ± 1.1 nm. All the films were optically transparent and had excellent adhesion based on the peel test. Indoor and accelerated weathering tests revealed good weathering stability.DOI: http://dx.doi.org/10.5755/j01.ms.22.2.12952

  3. Application of cationic hemicelluloses produced from corn husk as polyelectrolytes in sewage treatment

    Directory of Open Access Journals (Sweden)

    Alan Soares Landim

    2013-01-01

    Full Text Available Hemicelluloses were extracted from corn husk and converted into cationic hemicelluloses using 2,3-epoxypropyltrimethylammonium chloride. The degree of substitution was determined as 0.43 from results of elemental analysis. The cationic derivative was also characterized by Fourier transform infrared spectroscopy and Carbon-13 magnetic nuclear ressonance. The produced polymer was employed as coagulant aid in a sewage treatment station (STS of the municipal department of water and sewer (Departamento Municipal de Água e Esgoto - DMAE in Uberlândia-Minas Gerais, Brazil, using Jar test experiments. Its performance was compared to ACRIPOL C10, a commercial cationic polyacrylamide regularly used as a coagulant at the STS. The best result of the jar-test essays was obtained when using cationic hemicelluloses (10 mg L- 1 as coagulant aid and ferric chloride as coagulante (200 mg L- 1. The resultsof color and turbidity reduction, 37 and 39%, respectively, were better than when using only ferric chloride. These results were also higher than those of commercial polyacrylamide, on the order of 32.4 and 38.7%, respectively. The results showed that the cationic hemicelluloses presented similar or even superior performance when compared to ACRIPOL C10, demonstrating that the polyelectrolytes produced from recycled corn husks can replace commercial polymers in sewage treatment stations.

  4. Flocculation and redispersion of cellulosic fiber suspensions: A review of effects of hydrodynamic shear and polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Hubbe, M. A.

    2007-05-01

    Full Text Available Cellulosic fibers in aqueous suspensions are subject to flocculation effects that involve two contrasting scales of dimension. The net effect of flocculation determines how uniformly fibers can become formed into a sheet during the manufacture of paper. At a macroscopic level, the highly elongated shape of typical wood-derived fibers in agitated sus-pensions can give rise to frequent inter-fiber collisions and the formation of fiber flocs. At a submicroscopic scale, surfaces of suspended materials can become joined by macromolecular bridges. Although such bridges tend to reduce paper’s uniformity, polyelectrolyte flocculants are used in most paper machine systems to achieve relatively high retention efficiencies of fine particles as paper is being formed. By adjusting the papermaking equipment, judiciously selecting points of addition of chemicals, and by managing chemical dosages, papermakers employ a variety of strategies to achieve favorable combinations of retention and uniformity. This review considers scholarly work that has been directed towards a greater understanding of the underlying mechanisms.

  5. Simple and effective lumped mass models for determining kinetics and dynamics of car-to-car crashes

    NARCIS (Netherlands)

    Mooi, H.G.; Huibers, J.H.A.M.

    1998-01-01

    A simple two-mass-spring model was developed to describe the dynamics of car-to-car collisions. The characteristics of the spring in this model can be chosen as a piecewise linear function. The model was applied to determine the dynamics of a range of crashes and to compare the dynamics of a

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Climate Effects and Feedback Structure Determining Weed Population Dynamics in a Long-Term Experiment

    Science.gov (United States)

    Lima, Mauricio; Navarrete, Luis; González-Andujar, José Luis

    2012-01-01

    Pest control is one of the areas in which population dynamic theory has been successfully applied to solve practical problems. However, the links between population dynamic theory and model construction have been less emphasized in the management and control of weed populations. Most management models of weed population dynamics have emphasized the role of the endogenous process, but the role of exogenous variables such as climate have been ignored in the study of weed populations and their management. Here, we use long-term data (22 years) on two annual weed species from a locality in Central Spain to determine the importance of endogenous and exogenous processes (local and large-scale climate factors). Our modeling study determined two different feedback structures and climate effects in the two weed species analyzed. While Descurainia sophia exhibited a second-order feedback and low climate influence, Veronica hederifolia was characterized by a first-order feedback structure and important effects from temperature and rainfall. Our results strongly suggest the importance of theoretical population dynamics in understanding plant population systems. Moreover, the use of this approach, discerning between the effect of exogenous and endogenous factors, can be fundamental to applying weed management practices in agricultural systems and to controlling invasive weedy species. This is a radical change from most approaches currently used to guide weed and invasive weedy species managements. PMID:22272362

  11. Climate effects and feedback structure determining weed population dynamics in a long-term experiment.

    Science.gov (United States)

    Lima, Mauricio; Navarrete, Luis; González-Andujar, José Luis

    2012-01-01

    Pest control is one of the areas in which population dynamic theory has been successfully applied to solve practical problems. However, the links between population dynamic theory and model construction have been less emphasized in the management and control of weed populations. Most management models of weed population dynamics have emphasized the role of the endogenous process, but the role of exogenous variables such as climate have been ignored in the study of weed populations and their management. Here, we use long-term data (22 years) on two annual weed species from a locality in Central Spain to determine the importance of endogenous and exogenous processes (local and large-scale climate factors). Our modeling study determined two different feedback structures and climate effects in the two weed species analyzed. While Descurainia sophia exhibited a second-order feedback and low climate influence, Veronica hederifolia was characterized by a first-order feedback structure and important effects from temperature and rainfall. Our results strongly suggest the importance of theoretical population dynamics in understanding plant population systems. Moreover, the use of this approach, discerning between the effect of exogenous and endogenous factors, can be fundamental to applying weed management practices in agricultural systems and to controlling invasive weedy species. This is a radical change from most approaches currently used to guide weed and invasive weedy species managements.

  12. Climate effects and feedback structure determining weed population dynamics in a long-term experiment.

    Directory of Open Access Journals (Sweden)

    Mauricio Lima

    Full Text Available Pest control is one of the areas in which population dynamic theory has been successfully applied to solve practical problems. However, the links between population dynamic theory and model construction have been less emphasized in the management and control of weed populations. Most management models of weed population dynamics have emphasized the role of the endogenous process, but the role of exogenous variables such as climate have been ignored in the study of weed populations and their management. Here, we use long-term data (22 years on two annual weed species from a locality in Central Spain to determine the importance of endogenous and exogenous processes (local and large-scale climate factors. Our modeling study determined two different feedback structures and climate effects in the two weed species analyzed. While Descurainia sophia exhibited a second-order feedback and low climate influence, Veronica hederifolia was characterized by a first-order feedback structure and important effects from temperature and rainfall. Our results strongly suggest the importance of theoretical population dynamics in understanding plant population systems. Moreover, the use of this approach, discerning between the effect of exogenous and endogenous factors, can be fundamental to applying weed management practices in agricultural systems and to controlling invasive weedy species. This is a radical change from most approaches currently used to guide weed and invasive weedy species managements.

  13. Towards wafer scale inductive determination of magnetostatic and dynamic parameters of magnetic thin films and multilayers

    CERN Document Server

    Sievers, Sibylle; Nass, Paul; Serrano-Guisan, Santiago; Pasquale, Massimo; Schumacher, Hans Werner

    2013-01-01

    We investigate an inductive probe head suitable for non-invasive characterization of the magnetostatic and dynamic parameters of magnetic thin films and multilayers on the wafer scale. The probe is based on a planar waveguide with rearward high frequency connectors that can be brought in close contact to the wafer surface. Inductive characterization of the magnetic material is carried out by vector network analyzer ferromagnetic resonance. Analysis of the field dispersion of the resonance allows the determination of key material parameters such as the saturation magnetization MS or the effective damping parameter Meff. Three waveguide designs are tested. The broadband frequency response is characterized and the suitability for inductive determination of MS and Meff is compared. Integration of such probes in a wafer prober could in the future allow wafer scale in-line testing of magnetostatic and dynamic key material parameters of magnetic thin films and multilayers.

  14. Determination of Inelastic Mean Free Path by Electron Holography Along with Electron Dynamic Calculation

    Institute of Scientific and Technical Information of China (English)

    王岩国; 刘红荣; 杨奇斌; 张泽

    2003-01-01

    Off-axis electron holography in a field emission gun transmission-electron microscope and electron dynamic calculation are used to determine the absorption coefficient and inelastic mean free path (IMFP) of copper.Dependence of the phase shift of the exit electron wave on the specimen thickness is established by electron dynamic simulation. The established relationship makes it possible to determine the specimen thickness with the calculated phase shift by match of the phase shift measured in the reconstructed phase image. Based on the measured amplitudes in reconstructed exit electron wave and reference wave in the vacuum, the examined IMFP of electron with energy of 200kV in Cu is obtained to be 96nm.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Specific determination of benzene in urine using dynamic headspace and mass-selective detection.

    Science.gov (United States)

    Ljungkvist, G; Lärstad, M; Mathiasson, L

    1999-01-08

    A method for the determination of benzene in urine was developed, based on dynamic headspace and preconcentration of the analyte on a solid sorbent. The subsequent analysis by thermal desorption of the sorbent, capillary gas chromatography and mass-selective detection ascertained a low limit of detection (6.5 ng/l) and a highly specific determination. The limit of detection is an order of magnitude lower than that reported earlier and allows reliable quantitation of occupational exposure and of most environmental exposures. Samples could be stored frozen for at least a month without significant loss.

  10. Factors determining the diurnal dynamics of blooming of chosen plant species

    Directory of Open Access Journals (Sweden)

    Bożena Denisow

    2012-12-01

    Full Text Available The paper attempts to synthesize the determinants which may influence the diurnal rhythm of blooming. Additionally, I tried to explore and bring together topics that concern blooming and have always been considered separately because of their origin in different disciplines. The following species were included: Hydrangea arborescens L. subsp. discolor (Raf., H. paniculata Sieb., Viburnum opulus L., Chaenomeles japonica Lindl., Knautia arvensis L., Adonis vernalis L., Aster saggitifolius Willd., Taraxacum officinale L. Chelidonium majus L. The taxons were observed in Lublin (51008' - 51018' N and 21027' - 21041' E in the years 2001-2007. The blooming of species was determined at least for two vegetation seasons. During observations all flowers developed in one-hour intervals were counted. The diurnal dynamics of blooming differs among species and is modified by different endogenous and exogenous factors. The endogenous determinants of diurnal dynamics of blooming are morphological diversity of flowers (fertility or sterility within species or heterostyly. The different pattern of blooming succour different mechanisms which prevent self-pollination (Chaenomeles japonica Lindl., Knautia arvensis L.. The abiotic factors, such as day length and temperature during the vegetation season, influence the change in the process of diurnal dynamics of blooming (e. g. Taraxacum officinale, Chelidonium majus.

  11. Determination of Water Diffusion Coefficients and Dynamics in Adhesive/ Carbon Fiber Reinforced Epoxy Resin Composite Joints

    Institute of Scientific and Technical Information of China (English)

    WANG Chao; WANG Zhi; WANG Jing; SU Tao

    2007-01-01

    To determinate the water diffusion coefficients and dynamics in adhesive/carbon fiber reinforced epoxy resin composite joints, energy dispersive X-ray spectroscopy analysis(EDX) is used to establish the content change of oxygen in the adhesive in adhesive/carbon fiber reinforced epoxy resin composite joints. As water is made up of oxygen and hydrogen, the water diffusion coefficients and dynamics in adhesive/carbon fiber reinforced epoxy resin composite joints can be obtained from the change in the content of oxygen in the adhesive during humidity aging, via EDX analysis. The authors have calculated the water diffusion coefficients and dynamics in the adhesive/carbon fiber reinforced epoxy resin composite joints with the aid of both energy dispersive X-ray spectroscopy and elemental analysis. The determined results with EDX analysis are almost the same as those determined with elemental analysis and the results also show that the durability of the adhesive/carbon fiber reinforced epoxy resin composite joints subjected to silane coupling agent treatment is better than those subjected to sand paper burnishing treatment and chemical oxidation treatment.

  12. Determining dynamical parameters of the Milky Way Galaxy based on high-accuracy radio astrometry

    Science.gov (United States)

    Honma, Mareki; Nagayama, Takumi; Sakai, Nobuyuki

    2015-08-01

    In this paper we evaluate how the dynamical structure of the Galaxy can be constrained by high-accuracy VLBI (Very Long Baseline Interferometry) astrometry such as VERA (VLBI Exploration of Radio Astrometry). We generate simulated samples of maser sources which follow the gas motion caused by a spiral or bar potential, with their distribution similar to those currently observed with VERA and VLBA (Very Long Baseline Array). We apply the Markov chain Monte Carlo analyses to the simulated sample sources to determine the dynamical parameter of the models. We show that one can successfully determine the initial model parameters if astrometric results are obtained for a few hundred sources with currently achieved astrometric accuracy. If astrometric data are available from 500 sources, the expected accuracy of R0 and Θ0 is ˜ 1% or higher, and parameters related to the spiral structure can be constrained by an error of 10% or with higher accuracy. We also show that the parameter determination accuracy is basically independent of the locations of resonances such as corotation and/or inner/outer Lindblad resonances. We also discuss the possibility of model selection based on the Bayesian information criterion (BIC), and demonstrate that BIC can be used to discriminate different dynamical models of the Galaxy.

  13. Use of Direct Dynamics Simulations to Determine Unimolecular Reaction Paths and Arrhenius Parameters for Large Molecules.

    Science.gov (United States)

    Yang, Li; Sun, Rui; Hase, William L

    2011-11-08

    In a previous study (J. Chem. Phys.2008, 129, 094701) it was shown that for a large molecule, with a total energy much greater than its barrier for decomposition and whose vibrational modes are harmonic oscillators, the expressions for the classical Rice-Ramsperger-Kassel-Marcus (RRKM) (i.e., RRK) and classical transition-state theory (TST) rate constants become equivalent. Using this relationship, a molecule's unimolecular rate constants versus temperature may be determined from chemical dynamics simulations of microcanonical ensembles for the molecule at different total energies. The simulation identifies the molecule's unimolecular pathways and their Arrhenius parameters. In the work presented here, this approach is used to study the thermal decomposition of CH3-NH-CH═CH-CH3, an important constituent in the polymer of cross-linked epoxy resins. Direct dynamics simulations, at the MP2/6-31+G* level of theory, were used to investigate the decomposition of microcanonical ensembles for this molecule. The Arrhenius A and Ea parameters determined from the direct dynamics simulation are in very good agreement with the TST Arrhenius parameters for the MP2/6-31+G* potential energy surface. The simulation method applied here may be particularly useful for large molecules with a multitude of decomposition pathways and whose transition states may be difficult to determine and have structures that are not readily obvious.

  14. Pd(II)-Directed Encapsulation of Hydrogenase within the Layer-by-Layer Multilayers of Carbon Nanotube Polyelectrolyte Used as a Heterogeneous Catalyst for Oxidation of Hydrogen.

    Science.gov (United States)

    Liu, Jiang; Zorin, Nikolay A; Chen, Meng; Qian, Dong-Jin

    2015-06-16

    A metal-directed assembling approach has been developed to encapsulate hydrogenase (H2ase) within a layer-by-layer (LBL) multilayer of carbon nanotube polyelectrolyte (MWNT-PVPMe), which showed efficient biocatalytic oxidation of H2 gas. The MWNT-PVPMe was prepared via a diazonium process and addition reactions with poly(4-vinylpyridine) (PVP) and methyl iodide (MeI). The covalently attached polymers and organic substituents in the polyelectrolyte comprised 60-70% of the total weight. The polyelectrolyte was then used as a substrate for H2ase binding to produce MWNT-PVPMe@H2ase bionanocomposites. X-ray photoelectron spectra revealed that the bionanocomposites included the elements of Br, S, C, N, O, I, Fe, and Ni, which confirmed that they were composed of MWNT-PVPMe and H2ase. Field emission transmission electron microscope images revealed that the H2ase was adsorbed on the surface of MWNT-PVPMe with the domains ranging from 20 to 40 nm. Further, with the use of the bionanocomposites as nanolinkers and Na2PdCl4 as connectors, the (Pd/MWNT-PVPMe@H2ase)n multilayers were constructed on the quartz and gold substrate surfaces by the Pd(II)-directed LBL assembling technique. Finally, the as-prepared LBL multilayers were used as heterogeneous catalysts for hydrogen oxidation with methyl viologen (MV(2+)) as an electron carrier. The dynamic processes for the reversible color change between blue-colored MV(+) and colorless MV(2+) (catalyzed by the LBL multilayers) were video recorded, which confirmed that the H2ase encapsulated within the present LBL multilayers was of much stronger stability and higher biocatalytic activity of H2 oxidation resulting in potential applications for the development of H2 biosensors and fuel cells.

  15. Structural changes in a polyelectrolyte multilayer assembly investigated by reflection absorption infrared spectroscopy and sum frequency generation spectroscopy.

    Science.gov (United States)

    Kett, Peter J N; Casford, Michael T L; Yang, Amanda Y; Lane, Thomas J; Johal, Malkiat S; Davies, Paul B

    2009-02-12

    The structure of polyelectrolyte multilayer films adsorbed onto either a per-protonated or per-deuterated 11-mercaptoundecanoic acid (h-MUA/d-MUA) self assembled monolayer (SAM) on gold was investigated in air using two surface vibrational spectroscopy techniques, namely, reflection absorption infrared spectroscopy (RAIRS) and sum frequency generation (SFG) spectroscopy. Determination of film masses and dissipation values were made using a quartz crystal microbalance with dissipation monitoring (QCM-D). The films, containing alternating layers of the polyanion poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) and the polycation poly(ethylenimine) (PEI) built on the MUA SAM, were formed using the layer-by-layer electrostatic self-assembly method. The SFG spectrum of the SAM itself comprised strong methylene resonances, indicating the presence of gauche defects in the alkyl chains of the acid. The RAIRS spectrum of the SAM also contained strong methylene bands, indicating a degree of orientation of the methylene groups parallel to the surface normal. Changes in the SFG and RAIRS spectra when a PEI layer was adsorbed on the MUA monolayer showed that the expected electrostatic interaction between the polymer and the SAM, probably involving interpenetration of the PEI into the MUA monolayer, caused a straightening of the alkyl chains of the MUA and, consequently, a decrease in the number of gauche defects. When a layer of PAZO was subsequently deposited on the MUA/PEI film, further spectral changes occurred that can be explained by the formation of a complex PEI/PAZO interpenetrated layer. A per-deuterated MUA SAM was used to determine the relative contributions from the adsorbed polyelectrolytes and the MUA monolayer to the RAIRS and SFG spectra. Spectroscopic and adsorbed mass measurements combined showed that as further bilayers were constructed the interpenetration of PAZO into preadsorbed PEI layers was repeated, up to

  16. Using weigh-in-motion data to determine bridge dynamic amplification factor

    Directory of Open Access Journals (Sweden)

    Kalin Jan

    2015-01-01

    Full Text Available The dynamic component of bridge traffic loading is commonly taken into account with a Dynamic Amplification Factor (DAF – the ratio between the maximum dynamic and static load effects on a bridge. In the design codes, this factor is generally higher than in reality. While this is fine for new bridges that must account for various risks during their life-time, it imposes unnecessary conservativism into assessment of the existing well defined bridges. Therefore, analysis of existing bridges should apply more realistic DAF values. One way of obtaining them experimentally is by bridge weigh-in-motion (B-WIM measurements, which use an existing instrumented bridge or culvert to weigh all crossing vehicles at highway speeds. The B-WIM system had been equipped with two methods of obtaining an approximation to the static response of the. The first method uses the sum of influence lines. This method relies on accurate axle identification, the failure of which can have a large influence on the DAF value. The other method uses a pre-determined low-pass filter to remove the dynamic component of the measured signal; however an expert is needed to set the filter parameters. A new approach that tries to eliminate these two drawbacks has been developed. In this approach the parameters for the filter are determined automatically by fitting the filtered response to the sum of the influence lines. The measurement of DAF on a typical bridge site agrees with experiments performed in the ARCHES [1] project: dynamic amplification decreases as static loading increases.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. [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.

  7. 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.

  8. 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

  9. Determination of thermal/dynamic characteristics of lava flow from surface thermal measurements

    Science.gov (United States)

    Ismail-Zadeh, Alik; Melnik, Oleg; Korotkii, Alexander; Tsepelev, Igor; Kovtunov, Dmitry

    2016-04-01

    Rapid development of ground based thermal cameras, drones and satellite data allows getting repeated thermal images of the surface of the lava flow. Available instrumentation allows getting a large amount of data during a single lava flow eruption. These data require development of appropriate quantitative techniques to link subsurface dynamics with observations. We present a new approach to assimilation of thermal measurements at lava's surface to the bottom of the lava flow to determine lava's thermal and dynamic characteristics. Mathematically this problem is reduced to solving an inverse boundary problem. Namely, using known conditions at one part of the model boundary we determine the missing condition at the remaining part of the boundary. Using an adjoint method we develop a numerical approach to the mathematical problem based on the determination of the missing boundary condition and lava flow characteristics. Numerical results show that in the case of smooth input data lava temperature and velocity can be determined with a high accuracy. A noise imposed on the smooth input data results in a less accurate solution, but still acceptable below some noise level. The proposed approach to assimilate measured data brings an opportunity to estimate thermal budget of the lava flow.

  10. Bloodstain Pattern Analysis: implementation of a fluid dynamic model for position determination of victims

    Science.gov (United States)

    Laan, Nick; de Bruin, Karla G.; Slenter, Denise; Wilhelm, Julie; Jermy, Mark; Bonn, Daniel

    2015-06-01

    Bloodstain Pattern Analysis is a forensic discipline in which, among others, the position of victims can be determined at crime scenes on which blood has been shed. To determine where the blood source was investigators use a straight-line approximation for the trajectory, ignoring effects of gravity and drag and thus overestimating the height of the source. We determined how accurately the location of the origin can be estimated when including gravity and drag into the trajectory reconstruction. We created eight bloodstain patterns at one meter distance from the wall. The origin’s location was determined for each pattern with: the straight-line approximation, our method including gravity, and our method including both gravity and drag. The latter two methods require the volume and impact velocity of each bloodstain, which we are able to determine with a 3D scanner and advanced fluid dynamics, respectively. We conclude that by including gravity and drag in the trajectory calculation, the origin’s location can be determined roughly four times more accurately than with the straight-line approximation. Our study enables investigators to determine if the victim was sitting or standing, or it might be possible to connect wounds on the body to specific patterns, which is important for crime scene reconstruction.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Dynamic windowing algorithm for the fast and accurate determination of luminescence lifetimes.

    Science.gov (United States)

    Collier, Bradley B; McShane, Michael J

    2012-06-05

    An algorithm for the accurate calculation of luminescence lifetimes in near-real-time is described. The dynamic rapid lifetime determination (DRLD) method uses a window-summing technique and dynamically selects the appropriate window width for each lifetime decay such that a large range of lifetimes can be accurately calculated. The selection of window width is based on an optimal range of window-sum ratios. The algorithm was compared to alternative approaches for rapid lifetime determination as well as nonlinear least-squares (NLLS) fitting in both simulated and real experimental conditions. A palladium porphyrin was used as a model luminophore to quantitatively evaluate the algorithm in a dynamic situation, where oxygen concentration was modulated to induce a change in lifetime. Unlike other window-summing techniques, the new algorithm calculates lifetimes that are not significantly different than the slower, traditional NLLS. In addition, the computation time required to calculate the lifetime is 4 orders of magnitude less than NLLS and 2 orders less than other iterative methods. This advance will improve the accuracy of real-time measurements that must be made on samples that are expected to exhibit widely varying lifetimes, such as sensors and biosensors.

  16. Tracheomalacia in adults with cystic fibrosis: determination of prevalence and severity with dynamic cine CT.

    LENUS (Irish Health Repository)

    McDermott, Shaunagh

    2012-02-01

    PURPOSE: To determine the prevalence and severity of tracheomalacia in adults with cystic fibrosis (CF) by using dynamic cine multidetector computed tomography (CT) and to correlate these findings with pulmonary function test (PFT) results and the severity of parenchymal lung disease. MATERIALS AND METHODS: In this institutional review board-approved HIPAA-compliant study, 40 patients with CF (22 men, 18 women; mean age, 28 years +\\/- 8 [standard deviation]; age range, 18-54 years) prospectively underwent PFTs, standard thin-section CT, and two dynamic cine multidetector CT acquisitions. Ten control subjects underwent dynamic cine multidetector CT. After standard thin-section CT was completed, dynamic cine multidetector CT was performed during a forced expiratory maneuver and during coughing. Dynamic cine multidetector CT images in nine patients were excluded. Maximal inspiratory, dynamic expiratory, and end-expiratory tracheal luminal areas were compared (Student t test) and correlated (Spearman rank) with PFT results and severity of parenchymal lung disease. RESULTS: Mean predicted forced expiratory volume in 1 second (FEV(1)) was 70.6% +\\/- 20.7, and mean Bhalla CT score was 41.8% +\\/- 13.6. In patients with CF, dynamic cine mean tracheal cross-sectional area reduction was 51.7% +\\/- 18.4 (range, 9%-89%) for forced expiratory maneuvers and 68.8% +\\/- 11.7 (range, 18%-88%) for coughing (P = .001). Tracheomalacia was demonstrated in 24 (69%) patients and no control subjects during forced expiratory maneuvers (P = .001) and in 10 (29%) patients and one (10%) control subject during coughing. For end-expiration images, mean tracheal luminal reduction was 16.1% +\\/- 14.0% (range, 0.0%-53.0%), with one patient demonstrating tracheal luminal reduction of more than 50%. There was no correlation between tracheal cross-sectional luminal reduction and either predicted FEV(1) or CT Bhalla score. CONCLUSION: Tracheomalacia depicted at dynamic cine multidetector CT is a

  17. GPS Based Reduced-Dynamic Orbit Determination for Low Earth Orbiters with Ambiguity Fixing

    Directory of Open Access Journals (Sweden)

    Yang Yang

    2015-01-01

    Full Text Available With the ever-increasing number of satellites in Low Earth Orbit (LEO for scientific missions, the precise determination of the position and velocity of the satellite is a necessity. GPS (Global Positioning System based reduced-dynamic orbit determination (RPOD method is commonly used in the post processing with high precision. This paper presents a sequential RPOD strategy for LEO satellite in the framework of Extended Kalman Filter (EKF. Precise Point Positioning (PPP technique is used to process the GPS observations, with carrier phase ambiguity resolution using Integer Phase Clocks (IPCs products. A set of GRACE (Gravity Recovery And Climate Experiment mission data is used to test and validate the RPOD performance. Results indicate that orbit determination accuracy could be improved by 15% in terms of 3D RMS error in comparison with traditional RPOD method with float ambiguity solutions.

  18. Determination of the experimental equilibrium structure of solid nitromethane using path-integral molecular dynamics simulations

    Science.gov (United States)

    Reilly, Anthony M.; Habershon, Scott; Morrison, Carole A.; Rankin, David W. H.

    2010-03-01

    Path-integral molecular dynamics (PIMD) simulations with an empirical interaction potential have been used to determine the experimental equilibrium structure of solid nitromethane at 4.2 and 15 K. By comparing the time-averaged molecular structure determined in a PIMD simulation to the calculated minimum-energy (zero-temperature) molecular structure, we have derived structural corrections that describe the effects of thermal motion. These corrections were subsequently used to determine the equilibrium structure of nitromethane from the experimental time-averaged structure. We find that the corrections to the intramolecular and intermolecular bond distances, as well as to the torsion angles, are quite significant, particularly for those atoms participating in the anharmonic motion of the methyl group. Our results demonstrate that simple harmonic models of thermal motion may not be sufficiently accurate, even at low temperatures, while molecular simulations employing more realistic potential-energy surfaces can provide important insight into the role and magnitude of anharmonic atomic motions.

  19. Determination of a dynamic feeding strategy for recombinant Pichia pastoris strains.

    Science.gov (United States)

    Spadiut, Oliver; Dietzsch, Christian; Herwig, Christoph

    2014-01-01

    The knowledge of certain strain specific parameters of recombinant P. pastoris strains is required to be able to set up a feeding regime for fed-batch cultivations. To date, these parameters are commonly determined either by time-consuming and labor-intensive continuous cultivations or by several, consecutive fed-batch cultivations. Here, we describe a fast method based on batch experiments with methanol pulses to extract certain strain characteristic parameters, which are required to set up a dynamic feeding strategy for P. pastoris strains based on specific substrate uptake rate (q(s)). We further describe in detail the course of actions which have to be taken to obtain the desired dynamics during feeding.

  20. Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

    Science.gov (United States)

    Jaffe, Richard; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

  1. Aggregate size and structure determination of nanomaterials in physiological media: importance of dynamic evolution

    Science.gov (United States)

    Afrooz, A. R. M. Nabiul; Hussain, Saber M.; Saleh, Navid B.

    2014-12-01

    Most in vitro nanotoxicological assays are performed after 24 h exposure. However, in determining size and shape effect of nanoparticles in toxicity assays, initial characterization data are generally used to describe experimental outcome. The dynamic size and structure of aggregates are typically ignored in these studies. This brief communication reports dynamic evolution of aggregation characteristics of gold nanoparticles. The study finds that gradual increase in aggregate size of gold nanospheres (AuNS) occurs up to 6 h duration; beyond this time period, the aggregation process deviates from gradual to a more abrupt behavior as large networks are formed. Results of the study also show that aggregated clusters possess unique structural conformation depending on nominal diameter of the nanoparticles. The differences in fractal dimensions of the AuNS samples likely occurred due to geometric differences, causing larger packing propensities for smaller sized particles. Both such observations can have profound influence on dosimetry for in vitro nanotoxicity analyses.

  2. 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

  3. 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

  4. 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.

  5. 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)

  6. 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.

  7. 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.

  8. Using entropy maximization to understand the determinants of structural dynamics beyond native contact topology.

    Directory of Open Access Journals (Sweden)

    Timothy R Lezon

    2010-06-01

    Full Text Available Comparison of elastic network model predictions with experimental data has provided important insights on the dominant role of the network of inter-residue contacts in defining the global dynamics of proteins. Most of these studies have focused on interpreting the mean-square fluctuations of residues, or deriving the most collective, or softest, modes of motions that are known to be insensitive to structural and energetic details. However, with increasing structural data, we are in a position to perform a more critical assessment of the structure-dynamics relations in proteins, and gain a deeper understanding of the major determinants of not only the mean-square fluctuations and lowest frequency modes, but the covariance or the cross-correlations between residue fluctuations and the shapes of higher modes. A systematic study of a large set of NMR-determined proteins is analyzed using a novel method based on entropy maximization to demonstrate that the next level of refinement in the elastic network model description of proteins ought to take into consideration properties such as contact order (or sequential separation between contacting residues and the secondary structure types of the interacting residues, whereas the types of amino acids do not play a critical role. Most importantly, an optimal description of observed cross-correlations requires the inclusion of destabilizing, as opposed to exclusively stabilizing, interactions, stipulating the functional significance of local frustration in imparting native-like dynamics. This study provides us with a deeper understanding of the structural basis of experimentally observed behavior, and opens the way to the development of more accurate models for exploring protein dynamics.

  9. Dynamics of Determining Motives in Choosing the Medical Profession by Medical Students

    Directory of Open Access Journals (Sweden)

    Kloktunova N.A.

    2013-06-01

    Full Text Available The purpose of the article is to study motivation of students of medical schools in choice of profession of the doctor and dynamics of defining motives in educational space of university. Material and methods: 497 students of the 1 st course took part in comparative research (356 students of medical faculty and 141 students of pediatric faculty and 382 students of the 6th course (270 students of medical faculty and 112 students of pediatric faculty of Saratov state medical university n.a. V. I. Razumovsky. In research methods of questioning and statistical data processing have been used. Results: The comparative analysis of the maximum and minimum values of the main types of motivation in professional field choice allowed to determine leading motives in medical students, and also to reveal their dynamics connected with various stages of professionalizing in the course of receiving medical education. Conclusion: Professional self-determination of the student of medical school has a multi-vector focus of structure of motivation. Determination by internal motives is supplemented with influence of external motivation, both positive, and negative value. In students of the 6th course indicators of motives included «Prestige», «Opportunity to help people», «Possibility of use of professional skills out of work».

  10. Adaptive SLICE method: an enhanced method to determine nonlinear dynamic respiratory system mechanics.

    Science.gov (United States)

    Zhao, Zhanqi; Guttmann, Josef; Möller, Knut

    2012-01-01

    The objective of this paper is to introduce and evaluate the adaptive SLICE method (ASM) for continuous determination of intratidal nonlinear dynamic compliance and resistance. The tidal volume is subdivided into a series of volume intervals called slices. For each slice, one compliance and one resistance are calculated by applying a least-squares-fit method. The volume window (width) covered by each slice is determined based on the confidence interval of the parameter estimation. The method was compared to the original SLICE method and evaluated using simulation and animal data. The ASM was also challenged with separate analysis of dynamic compliance during inspiration. If the signal-to-noise ratio (SNR) in the respiratory data decreased from +∞ to 10 dB, the relative errors of compliance increased from 0.1% to 22% for the ASM and from 0.2% to 227% for the SLICE method. Fewer differences were found in resistance. When the SNR was larger than 40 dB, the ASM delivered over 40 parameter estimates (42.2 ± 1.3). When analyzing the compliance during inspiration separately, the estimates calculated with the ASM were more stable. The adaptive determination of slice bounds results in consistent and reliable parameter values. Online analysis of nonlinear respiratory mechanics will profit from such an adaptive selection of interval size.

  11. Elucidating the Role of Conjugated Polyelectrolyte Interlayers for High-Efficiency Organic Photovoltaics.

    Science.gov (United States)

    Lim, Kyung-Geun; Park, Sung Min; Woo, Han Young; Lee, Tae-Woo

    2015-09-21

    Despite the promising function of conjugated polyelectrolytes (CPEs) as an interfacial layer in organic photovoltaics (OPVs), the underlying mechanism of dipole orientation and the electrical characteristics of CPE interlayers remain unclear. Currently, the ionic functionality of CPEs (i.e., whether they are cationic or anionic) is believed to determine the interfacial dipole alignment and the resulting electron or hole extraction properties at the interface between an organic photoactive layer and a metal electrode. In this research, we find that in contrast to this common belief, the photovoltaic efficiency can be improved significantly by both cationic and anionic CPE layers regardless of the ion functionality of the CPE. This improvement occurs because the interfacial dipoles of cationic and anionic CPEs are realigned in the identical direction despite the different ionic functionality. The net dipole is determined not by the intrinsic molecular dipole of the CPE but by the ionic redistribution in the CPE layer and the resulting interfacial dipole at the intimate contact with adjacent layers. We also demonstrated that the energy level alignment and performance parameters of OPVs can be controlled systematically by the electrically poled CPE layers with the oriented interfacial dipoles; the distribution of positive and negative ions in the CPE layer was adjusted by applying an appropriate external electric field, and the energy alignment was reversible by changing the electric field direction. The anionic and cationic CPEs (PSBFP-Na and PAHFP-Br) based on the same π-conjugated backbone of fluorene-phenylene were each used as the electron extraction layer on a photoactive layer. Both anionic and cationic CPE interlayers improved the energy level alignment at the interface between the photoactive layer and the electrode and the resulting performance parameters, which thereby increased the power conversion efficiency to 8.3 %.

  12. Immediate postarousal sleep dynamics: an important determinant of sleep stability in obstructive sleep apnea.

    Science.gov (United States)

    Younes, Magdy; Hanly, Patrick J

    2016-04-01

    Arousability from sleep is increasingly recognized as an important determinant of the clinical spectrum of sleep disordered breathing (SDB). Patients with SDB display a wide range of arousability. The reason for these differences is not known. We hypothesized that differences in the speed with which sleep deepens following arousals/awakenings (postarousal sleep dynamics) is a major determinant of these differences in arousability in patients with SDB. We analyzed 40 preexisting clinical polysomnography records from patients with a range of SDB severity (apnea-hypopnea index 5-135/h). Sleep depth was determined every 3 s using the odds ratio product (ORP) method, a continuous index of sleep depth (0 = deep sleep, 2.5 = full wakefulness) that correlates strongly (r = 0.98) with arousability (Younes M, Ostrowski M, Soiferman M, Younes H, Younes M, Raneri J, and Hanly P. Sleep 38: 641-654, 2015). Time course of ORP was determined from end of arousal until the next arousal. All arousals were analyzed (142 ± 65/polysomnogram). ORP increased from 0.58 ± 0.32 during sleep to 1.67 ± 0.35 during arousals. ORP immediately (first 9 s) following arousals/awakenings (ORP-9) ranged from 0.21(very deep sleep) to 1.71 (highly arousable state) in different patients. In patients with high ORP-9, sleep deepened slowly (over minutes) beyond 9 s but only if no arousals/awakenings recurred. ORP-9 correlated strongly with average non-rapid eye movement sleep depth (r = 0.87, P sleep architecture. We conclude that postarousal sleep dynamics are highly variable among patients with sleep-disordered breathing and largely determine average sleep depth and continuity.

  13. Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids

    DEFF Research Database (Denmark)

    Toxværd, Søren; Dyre, J. C.

    2011-01-01

    . Lett. 103, 170601 (2009);10.1103/PhysRevLett.103.170601 J. Chem. Phys. 134, 214503 (2011)10.1063/1.3592709] . We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations......The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev...

  14. Water Dispersible and Biocompatible Porphyrin-Based Nanospheres for Biophotonics Applications: A Novel Surfactant and Polyelectrolyte-Based Fabrication Strategy for Modifying Hydrophobic Porphyrins.

    Science.gov (United States)

    Sheng, Ning; Zong, Shenfei; Cao, Wei; Jiang, Jianzhuang; Wang, Zhuyuan; Cui, Yiping

    2015-09-01

    The hydrophobility of most porphyrin and porphyrin derivatives has limited their applications in medicine and biology. Herein, we developed a novel and general strategy for the design of porphyrin nanospheres with good biocompatibility and water dispersibility for biological applications using hydrophobic porphyrins. In order to display the generality of the method, we used two hydrophobic porphyrin isomers as starting material which have different structures confirmed by an X-ray technique. The porphyrin nanospheres were fabricated through two main steps. First, the uniform porphyrin nanospheres stabilized by surfactant were prepared by an interfacially driven microemulsion method, and then the layer-by-layer method was used for the synthesis of polyelectrolyte-coated porphyrin nanospheres to reduce the toxicity of the surfactant as well as improve the biocompatibility of the nanospheres. The newly fabricated porphyrin nanospheres were characterized by TEM techniques, the electronic absorption spectra, photoluminescence emission spectra, dynamic light scattering, and cytotoxicity examination. The resulting nanospheres demonstrated good biocompatibility, excellent water dispersibility and low toxicity. In order to show their application in biophotonics, these porphyrin nanospheres were successfully applied in targeted living cancer cell imaging. The results showed an effective method had been explored to prepare water dispersible and highly stable porphyrin nanomaterial for biophotonics applications using hydrophobic porphyrin. The approach we reported shows obvious flexibility because the surfactants and polyelectrolytes can be optionally selected in accordance with the characteristics of the hydrophobic material. This strategy will expand the applications of hydrophobic porphyrins owning excellent properties in medicine and biology.

  15. A Dynamic Analysis of the Determinants of the Greek Credit Default Swaps

    Directory of Open Access Journals (Sweden)

    Maria do Rosario CORREIA

    2016-06-01

    Full Text Available Abstract. There is a consensus in finance literature that credit default swap spreads can be used to calculate the default probability of a government bond. The question is therefore what determines the credit default swap spreads and also what is a good indicator that predicts the future behaviour of this security spreads. In this paper, we investigate several variables which have been used in the past to predict the CDS spreads. We do this by analysing the behaviour of credit swaps spreads of Greek sovereign debt over the recent financial crisis. We take into account the changes on the data generating process as the crisis evolves. Moreover, we also investigate which part of the dynamic process of CDS spreads is explained by each possible determinant. In order to do so, we use a time-frequency approach. As it turns out, some determinants are better in explaining the short term behaviour of the CDS spreads whilst others explain the long term behaviour. We can also say by how many months one factor determines the behaviour of the CDS spreads for Greek sovereign debt. With this information we are able to determine the probability of default and what it depends upon..Keywords. Eurozone crisis, Government default, Greek default, Credit default swap, Default probability.JEL. C22, C58, G14, G15, H63, H68.

  16. Habitat heterogeneity determines climate impact on zooplankton community structure and dynamics.

    Directory of Open Access Journals (Sweden)

    Saskia A Otto

    Full Text Available Understanding and predicting species distribution in space and time and consequently community structure and dynamics is an important issue in ecology, and particularly in climate change research. A crucial factor determining the composition and dynamics of animal populations is habitat heterogeneity, i.e., the number of structural elements in a given locality. In the marine pelagic environment habitat heterogeneity is represented by the distribution of physical oceanographic parameters such as temperature, salinity and oxygen that are closely linked to atmospheric conditions. Little attention has been given, however, to the role of habitat heterogeneity in modulating the response of animal communities to external climate forcing. Here we investigate the long-term dynamics of Acartia spp., Temora longicornis, and Pseudocalanus acuspes, three dominant zooplankton species inhabiting different pelagic habitats in the Central Baltic Sea (CBS. We use the three copepods as indicator species for changes in the CBS zooplankton community and apply non-linear statistical modeling techniques to compare spatial population trends and to identify their drivers. We demonstrate that effects of climate variability and change depend strongly on species-specific habitat utilization, being more direct and pronounced at the upper water layer. We propose that the differential functional response to climate-related drivers in relation to strong habitat segregation is due to alterations of the species' environmental niches. We stress the importance of understanding how anticipated climate change will affect ecological niches and habitats in order to project spatio-temporal changes in species abundance and distribution.

  17. Main Effect QTL with Dominance Determines Heterosis for Dynamic Plant Height in Upland Cotton.

    Science.gov (United States)

    Shang, Lianguang; Ma, Lingling; Wang, Yumei; Su, Ying; Wang, Xiaocui; Li, Yuhua; Abduweli, Abdugheni; Cai, Shihu; Liu, Fang; Wang, Kunbo; Hua, Jinping

    2016-10-13

    Plant height, which shows dynamic development and heterosis, is a major trait affecting plant architecture and has an indirect influence on economic yield related to biological yield in cotton. In the present study, we carried out dynamic analysis for plant height and its heterosis by quantitative trait loci (QTL) mapping at multiple developmental stages using two recombinant inbred lines (RILs) and their backcross progeny. At the single-locus level, 47 QTL were identified at five developmental stages in two hybrids. In backcross populations, QTL identified at an early stage mainly showed partial effects and QTL detected at a later stage mostly displayed overdominance effects. At the two-locus level, we found that main effect QTL played a more important role than epistatic QTL in the expression of heterosis in backcross populations. Therefore, this study implies that the genetic basis of plant height heterosis shows dynamic character and main effect QTL with dominance determines heterosis for plant height in Upland cotton. Copyright © 2016 Shang et al.

  18. Main Effect QTL with Dominance Determines Heterosis for Dynamic Plant Height in Upland Cotton

    Directory of Open Access Journals (Sweden)

    Lianguang Shang

    2016-10-01

    Full Text Available Plant height, which shows dynamic development and heterosis, is a major trait affecting plant architecture and has an indirect influence on economic yield related to biological yield in cotton. In the present study, we carried out dynamic analysis for plant height and its heterosis by quantitative trait loci (QTL mapping at multiple developmental stages using two recombinant inbred lines (RILs and their backcross progeny. At the single-locus level, 47 QTL were identified at five developmental stages in two hybrids. In backcross populations, QTL identified at an early stage mainly showed partial effects and QTL detected at a later stage mostly displayed overdominance effects. At the two-locus level, we found that main effect QTL played a more important role than epistatic QTL in the expression of heterosis in backcross populations. Therefore, this study implies that the genetic basis of plant height heterosis shows dynamic character and main effect QTL with dominance determines heterosis for plant height in Upland cotton.

  19. DETERMINATION OF PROMINENCE PLASMA {beta} FROM THE DYNAMICS OF RISING PLUMES

    Energy Technology Data Exchange (ETDEWEB)

    Hillier, Andrew [Kwasan and Hida Observatories, Kyoto University, Kyoto (Japan); Hillier, Richard [Department of Aeronautics, Imperial College, London (United Kingdom); Tripathi, Durgesh, E-mail: andrew@kwasan.kyoto-u.ac.jp [Inter-University Centre for Astronomy and Astrophysics, Post Bag 4, Ganeshkhind, Pune 411 007 (India)

    2012-12-20

    Observations by the Hinode satellite show in great detail the dynamics of rising plumes, dark in chromospheric lines, in quiescent prominences that propagate from large ({approx}10 Mm) bubbles that form at the base of the prominences. These plumes present a very interesting opportunity to study magnetohydrodynamic (MHD) phenomena in quiescent prominences, but obstacles still remain. One of the biggest issues is that of the magnetic field strength, which is not easily measurable in prominences. In this paper we present a method that may be used to determine a prominence's plasma {beta} when rising plumes are observed. Using the classic fluid dynamic solution for flow around a circular cylinder with an MHD correction, the compression of the prominence material can be estimated. This has been successfully confirmed through simulations; application to a prominence gave an estimate of the plasma {beta} as {beta} = 0.47 {+-} 0.079 to 1.13 {+-} 0.080 for the range {gamma} = 1.4-1.7. Using this method it may be possible to estimate the plasma {beta} of observed prominences, therefore helping our understanding of a prominence's dynamics in terms of MHD phenomena.

  20. Determination of Dynamics of Plant Plasma Membrane Proteins with Fluorescence Recovery and Raster Image Correlation Spectroscopy.

    Science.gov (United States)

    Laňková, Martina; Humpolíčková, Jana; Vosolsobě, Stanislav; Cit, Zdeněk; Lacek, Jozef; Čovan, Martin; Čovanová, Milada; Hof, Martin; Petrášek, Jan

    2016-04-01

    A number of fluorescence microscopy techniques are described to study dynamics of fluorescently labeled proteins, lipids, nucleic acids, and whole organelles. However, for studies of plant plasma membrane (PM) proteins, the number of these techniques is still limited because of the high complexity of processes that determine the dynamics of PM proteins and the existence of cell wall. Here, we report on the usage of raster image correlation spectroscopy (RICS) for studies of integral PM proteins in suspension-cultured tobacco cells and show its potential in comparison with the more widely used fluorescence recovery after photobleaching method. For RICS, a set of microscopy images is obtained by single-photon confocal laser scanning microscopy (CLSM). Fluorescence fluctuations are subsequently correlated between individual pixels and the information on protein mobility are extracted using a model that considers processes generating the fluctuations such as diffusion and chemical binding reactions. As we show here using an example of two integral PM transporters of the plant hormone auxin, RICS uncovered their distinct short-distance lateral mobility within the PM that is dependent on cytoskeleton and sterol composition of the PM. RICS, which is routinely accessible on modern CLSM instruments, thus represents a valuable approach for studies of dynamics of PM proteins in plants.

  1. THE DYNAMICS OF STUDENTS’ PROFESSIONAL SELF-DETERMINATION VALUE ORIENTATION (THE SOCIOLOGICAL ASPECT

    Directory of Open Access Journals (Sweden)

    Evgeniya Vladislavovna Yarina

    2014-10-01

    Full Text Available The article is devoted to the issues of students’ professional self-determination in the university community. It represents empirical analysis of the dynamics of professional value orientation of students in the period of  2005– 2013 as exemplified by the students of Moscow state university of railway engineering .The analysis revealed the motives for choice and the evaluation of the potential of the profession, the youngsters are studying for  in the university. The results of the research in certainty and expectations of the students in terms of employment are compared to the official statistic in the recruitment sphere.  The article also represented clearly defined conditions necessary for the provision of the successful formation of the professional self-determination in tertiary education.

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. PREFACE: Structure and dynamics determined by neutron and x-ray scattering Structure and dynamics determined by neutron and x-ray scattering

    Science.gov (United States)

    Müller-Buschbaum, Peter

    2011-06-01

    Neutron and x-ray scattering have emerged as powerful methods for the determination of structure and dynamics. Driven by emerging new, powerful neutron and synchrotron radiation sources, the continuous development of new instrumentation and novel scattering techniques gives rise to exciting possibilities. For example, in situ observations become possible via a high neutron or x-ray flux at the sample and, as a consequence, morphological transitions with small time constants can be detected. This special issue covers a broad range of different materials from soft to hard condensed matter. Hence, different material classes such as colloids, polymers, alloys, oxides and metals are addressed. The issue is dedicated to the 60th birthday of Professor Winfried Petry, scientific director of the Research Neutron Source Heinz Maier-Leibnitz (FRM-II), Germany, advisor at the physics department for the Bayerische Elite-Akademie, chair person of the Arbeitsgemeinschaft Metall- und Materialphysik of the German Physical Society (DPG) and a member of the professional council of the German Science Foundation (Deutsche Forschungsgemeinschaft, DFG). We would like to acknowledge and thank all contributors for their submissions, which made this special issue possible in the first place. Moreover, we would like to thank the staff at IOP Publishing for helping us with the administrative aspects and for coordinating the refereeing process, and Valeria Lauter for the beautiful cover artwork. Finally, to the readers, we hope that you find this special issue a valuable resource that provides insights into the present possibilities of neutron and x-ray scattering as powerful tools for the investigation of structure and dynamics. Structure and dynamics determined by neutron and x-ray scattering contents In situ studies of mass transport in liquid alloys by means of neutron radiography F Kargl, M Engelhardt, F Yang, H Weis, P Schmakat, B Schillinger, A Griesche and A Meyer Magnetic spin

  18. The interaction of intrinsic dynamics and network topology in determining network burst synchrony.

    Science.gov (United States)

    Gaiteri, Chris; Rubin, Jonathan E

    2011-01-01

    The pre-Bötzinger complex (pre-BötC), within the mammalian respiratory brainstem, represents an ideal system for investigating the synchronization properties of complex neuronal circuits via the interaction of cell-type heterogeneity and network connectivity. In isolation, individual respiratory neurons from the pre-BötC may be tonically active, rhythmically bursting, or quiescent. Despite this intrinsic heterogeneity, coupled networks of pre-BötC neurons en bloc engage in synchronized bursting that can drive inspiratory motor neuron activation. The region's connection topology has been recently characterized and features dense clusters of cells with occasional connections between clusters. We investigate how the dynamics of individual neurons (quiescent/bursting/tonic) and the betweenness centrality of neurons' positions within the network connectivity graph interact to govern network burst synchrony, by simulating heterogeneous networks of computational model pre-BötC neurons. Furthermore, we compare the prevalence and synchrony of bursting across networks constructed with a variety of connection topologies, analyzing the same collection of heterogeneous neurons in small-world, scale-free, random, and regularly structured networks. We find that several measures of network burst synchronization are determined by interactions of network topology with the intrinsic dynamics of neurons at central network positions and by the strengths of synaptic connections between neurons. Surprisingly, despite the functional role of synchronized bursting within the pre-BötC, we find that synchronized network bursting is generally weakest when we use its specific connection topology, which leads to synchrony within clusters but poor coordination across clusters. Overall, our results highlight the relevance of interactions between topology and intrinsic dynamics in shaping the activity of networks and the concerted effects of connectivity patterns and dynamic heterogeneities.

  19. The role of self-determined motivation in job search: A dynamic approach.

    Science.gov (United States)

    da Motta Veiga, Serge P; Gabriel, Allison S

    2016-03-01

    Job search is a dynamic self-regulated process during which job seekers need to stay motivated to secure a job. However, past research has taken a relatively static approach to examining motivation during the job search, in addition to ignoring how the quality of one's motivation--ranging from autonomous to controlled--can influence job search processes. Adopting a within-person perspective, the current study extends self-determination theory (SDT) to the job search context to investigate (a) when autonomous and controlled motivations are more or less prevalent and (b) whether they influence job search effort through metacognitive strategies in differing ways depending upon the amount of time elapsed in the search. In a weekly study of new labor market entrants (Level-2 n = 149; Level-1 n = 691), results indicated that autonomous motivation decreased until the midpoint of the job search and then plateaued, whereas controlled motivation remained stable. Results also showed that autonomous motivation had a consistent, positive relation with metacognitive strategies, whereas the relation between controlled motivation and such strategies was negative early in the job search, but became positive as the job search progressed. Finally, the effects of motivation on job search effort occurred via metacognitive strategies differentially depending upon the time elapsed in the search. Combined, we provide a first glimpse into the dynamics of self-determined motivation on job search processes. (c) 2016 APA, all rights reserved).

  20. Determining the number of kanbans for dynamic production systems: An integrated methodology

    Directory of Open Access Journals (Sweden)

    Özlem Uzun Araz

    2016-08-01

    Full Text Available Just-in-time (JIT is a management philosophy that reduces the inventory levels and eliminates manufacturing wastes by producing only the right quantity at the right time. A kanban system is one of the key elements of JIT philosophy. Kanbans are used to authorize production and to control movement of materials in JIT systems. In Kanban systems, the efficiency of the manufacturing system depends on several factors such as number of kanbans, container size etc. Hence, determining the number of kanbans is a critical decision in Kanban systems. The aim of this study is to develop a methodology that can be used in order to determine the number of kanbans in a dynamic production environment. In this methodology, the changes in system state is monitored in real time manner, and the number of the kanbans are dynamically re-arranged. The proposed methodology integrates simulation, neural networks and Mamdani type fuzzy inference system. The methodology is modelled in simulation environment and applied on a hypothetic production system. We also performed several comparisons for different control policies to show the effectiveness of the proposed methodology.

  1. Inverse Force Determination on a Small Scale Launch Vehicle Model Using a Dynamic Balance

    Science.gov (United States)

    Ngo, Christina L.; Powell, Jessica M.; Ross, James C.

    2017-01-01

    A launch vehicle can experience large unsteady aerodynamic forces in the transonic regime that, while usually only lasting for tens of seconds during launch, could be devastating if structural components and electronic hardware are not designed to account for them. These aerodynamic loads are difficult to experimentally measure and even harder to computationally estimate. The current method for estimating buffet loads is through the use of a few hundred unsteady pressure transducers and wind tunnel test. Even with a large number of point measurements, the computed integrated load is not an accurate enough representation of the total load caused by buffeting. This paper discusses an attempt at using a dynamic balance to experimentally determine buffet loads on a generic scale hammer head launch vehicle model tested at NASA Ames Research Center's 11' x 11' transonic wind tunnel. To use a dynamic balance, the structural characteristics of the model needed to be identified so that the natural modal response could be and removed from the aerodynamic forces. A finite element model was created on a simplified version of the model to evaluate the natural modes of the balance flexures, assist in model design, and to compare to experimental data. Several modal tests were conducted on the model in two different configurations to check for non-linearity, and to estimate the dynamic characteristics of the model. The experimental results were used in an inverse force determination technique with a psuedo inverse frequency response function. Due to the non linearity, the model not being axisymmetric, and inconsistent data between the two shake tests from different mounting configuration, it was difficult to create a frequency response matrix that satisfied all input and output conditions for wind tunnel configuration to accurately predict unsteady aerodynamic loads.

  2. Effect of Film-Forming Alginate/Chitosan Polyelectrolyte Complex on the Storage Quality of Pork

    Directory of Open Access Journals (Sweden)

    Dominika Kulig

    2017-01-01

    Full Text Available Meat is one of the most challenging food products in the context of maintaining quality and safety. The aim of this work was to improve the quality of raw/cooked meat by coating it with sodium alginate (A, chitosan (C, and sodium alginate-chitosan polyelectrolyte complex (PEC hydrosols. Antioxidant properties of A, C, and PEC hydrosols were determined. Subsequently, total antioxidant capacity (TAC, sensory quality of raw/cooked pork coated with experimental hydrosols, and antimicrobial efficiency of those hydrosols on the surface microbiota were analysed. Application analyses of hydrosol were performed during 0, 7, and 14 days of refrigerated storage in MAP (modified atmosphere packaging. Ferric reducing antioxidant power (FRAP and (2,2-diphenyll-picrylhydrazyl (DPPH analysis confirmed the antioxidant properties of A, C, and PEC. Sample C (1.0% was characterized by the highest DPPH value (174.67 μM Trolox/mL of all variants. PEC samples consisted of A 0.3%/C 1.0% and A 0.6%/C 1.0% were characterized by the greatest FRAP value (~7.21 μM Fe2+/mL of all variants. TAC losses caused by thermal treatment of meat were reduced by 45% by coating meat with experimental hydrosols. Application of PEC on the meat surface resulted in reducing the total number of micro-organisms, psychrotrophs, and lactic acid bacteria by about 61%, and yeast and molds by about 45% compared to control after a two-week storage.

  3. Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

    Science.gov (United States)

    Pacalin, Naomi M.; Leon, Lorraine; Tirrell, Matthew

    2016-10-01

    Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained β-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer

  4. ζ-potential determination using a ZetaMeter-Dynamic Speckle assembly

    Science.gov (United States)

    González-Peña, Rolando J.; Sánchez-Muñoz, Orlando L.; Martínez-Celorio, René A.; Cibrián, Rosa M.; Salvador-Palmer, Rosario; Salgado, Jesús

    2012-10-01

    Electrophoretic mobility and ζ-potential are important physical parameters for the characterization of micro- and nanosystems. In this communication we describe a new method for determining the ζ-potential through the assembly of two well known techniques: free electrophoresis and Dynamic Speckle. When coherent light passes through a fluid having scattering centres, the far field interference originates a speckled image. If the scattering centres are contained within the cylindrical electrophoresis cell of a ZetaMeter and are forced to move in an orderly way under the action of an external electric field, the time variation of the light intensity in the far field speckle images follows a temporal autocorrelation function g(τ). The corresponding correlation time can then be obtained and related with the velocity, from which the electrophoretic mobility and the ζ-potential of the scattering centres can be determined. We have applied this method to microparticles, like natural air-floated silica and two classes of bioceramics, hydroxyapatite and biphasic calcium phosphate. For comparison, we analysed the same samples in parallel using a commercial Zetasizer Nano from Malvern Instruments. The values of ζ-potential determined using the two techniques were the same within ~3% error. These results validate our new method as a useful and efficient alternative for ζ-potential determination of particles, at least within the micrometer scale.

  5. A Dynamic Analysis on Determining of Housing Demand: A Comparison for Turkey, Hungary, and UK

    Institute of Scientific and Technical Information of China (English)

    Selahattin Bekmez; Ash Ozpolat

    2014-01-01

    Housing is both good and investment assets so that it plays an important role in the economy. Housing also can be characterized the most complex economic good because of its durability, heterogeneity, locational fixity, the possibility to raise loans against housing collateral, and the effect on well-developed secondary markets. On the other hand, income distribution, socio-economic justice, and regional disparities imply that housing market is an important concept for social and cultural transformation. In this study, the determinants of housing demand were compared for countries. These countries are selected according to economic situation: Turkey, Hungary, and United Kingdom. As a scope of this, the dynamic relationship between the housing demand and variables determining the housing demand in Turkey, Hungary, and UK has been analyzed. The model estimated uses quarterly data from January 2002 to January 2014. Building permits has been considered as housing demand. The other variables used for determining the housing demand are GDP, monetary aggregate, interest rate, and share prices. The long term relationship among variables has been analyzed with Vector Autoregressive Model (VAR) as impulse response and variance decomposition. The findings indicate that determining of housing demand changes according to economic and financial components such as government policies, mortgage system, consumer choice, tax, and subsidy in selected countries. All variables play an important role in housing demand, although the level of their impacts varies.

  6. 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.

  7. 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.

  8. 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.

  9. A theoretical framework for determining cerebral vascular function and heterogeneity from dynamic susceptibility contrast MRI.

    Science.gov (United States)

    Digernes, Ingrid; Bjørnerud, Atle; Vatnehol, Svein Are S; Løvland, Grete; Courivaud, Frédéric; Vik-Mo, Einar; Meling, Torstein R; Emblem, Kyrre E

    2017-06-01

    Mapping the complex heterogeneity of vascular tissue in the brain is important for understanding cerebrovascular disease. In this translational study, we build on previous work using vessel architectural imaging (VAI) and present a theoretical framework for determining cerebral vascular function and heterogeneity from dynamic susceptibility contrast magnetic resonance imaging (MRI). Our tissue model covers realistic structural architectures for vessel branching and orientations, as well as a range of hemodynamic scenarios for blood flow, capillary transit times and oxygenation. In a typical image voxel, our findings show that the apparent MRI relaxation rates are independent of the mean vessel orientation and that the vortex area, a VAI-based parameter, is determined by the relative oxygen saturation level and the vessel branching of the tissue. Finally, in both simulated and patient data, we show that the relative distributions of the vortex area parameter as a function of capillary transit times show unique characteristics in normal-appearing white and gray matter tissue, whereas tumour-voxels in comparison display a heterogeneous distribution. Collectively, our study presents a comprehensive framework that may serve as a roadmap for in vivo and per-voxel determination of vascular status and heterogeneity in cerebral tissue.

  10. Determination of the protonation state of the Asp dyad: conventional molecular dynamics versus thermodynamic integration.

    Science.gov (United States)

    Huang, Jinfeng; Zhu, Yali; Sun, Bin; Yao, Yuan; Liu, Junjun

    2016-03-01

    The protonation state of the Asp dyad is important as it can reveal enzymatic mechanisms, and the information this provides can be used in the development of drugs for proteins such as memapsin 2 (BACE-1), HIV-1 protease, and rennin. Conventional molecular dynamics (MD) simulations have been successfully used to determine the preferred protonation state of the Asp dyad. In the present work, we demonstrate that the results obtained from conventional MD simulations can be greatly influenced by the particular force field applied or the values used for control parameters. In principle, free-energy changes between possible protonation states can be used to determine the protonation state. We show that protonation state prediction by the thermodynamic integration (TI) method is insensitive to force field version or to the cutoff for calculating nonbonded interactions (a control parameter). In the present study, the protonation state of the Asp dyad predicted by TI calculations was the same regardless of the force field and cutoff value applied. Contrary to the intuition that conventional MD is more efficient, our results clearly show that the TI method is actually more efficient and more reliable for determining the protonation state of the Asp dyad.

  11. Determination of boron over a large dynamic range by prompt-gamma activation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Harrison, R.K. [University of Texas at Austin, Nuclear Engineering Teaching Lab., Pickle Research Campus, R-9000 Austin, TX 78712 (United States); Landsberger, S. [University of Texas at Austin, Nuclear Engineering Teaching Lab., Pickle Research Campus, R-9000 Austin, TX 78712 (United States)], E-mail: s.landsberger@mail.utexas.edu

    2009-02-15

    An evaluation of the PGAA method for the determination of boron across a wide dynamic range of concentrations was performed for trace levels up to 5 wt.% boron. This range encompasses a transition from neutron transparency to significant self- shielding conditions. To account for self-shielding, several PGAA techniques were employed. First, a calibration curve was developed in which a set of boron standards was tested and the count rate to boron mass curve was determined. This set of boron measurements was compared with an internal standard self-shielding correction method and with a method for determining composition using PGAA peak ratios. The advantages and disadvantages of each method are analyzed. The boron concentrations of several laboratory-grade chemicals and standard reference materials were measured with each method and compared. The evaluation of the boron content of nanocrystalline transition metals prepared with a boron-containing reducing agent was also performed with each of the methods tested. Finally, the k{sub 0} method was used for non-destructive measurement of boron in catalyst materials for the characterization of new non-platinum fuel cell catalysts.

  12. Methodology to determine failure characteristics of planar soft tissues using a dynamic tensile test.

    Science.gov (United States)

    Jacquemoud, C; Bruyere-Garnier, K; Coret, M

    2007-01-01

    Predicting the injury risk in automotive collisions requires accurate knowledge of human tissues, more particularly their mechanical properties under dynamic loadings. The present methodology aims to determine the failure characteristics of planar soft tissues such as skin, hollow organs and large vessel walls. This consists of a dynamic tensile test, which implies high-testing velocities close to those in automotive collisions. To proceed, I-shaped tissue samples are subjected to dynamic tensile tests using a customized tensile device based on the drop test principle. Data acquisition has especially been adapted to heterogeneous and soft biological tissues given that standard measurement systems (considered to be global) have been completed with a non-contact and full-field strain measurement (considered to be local). This local measurement technique, called the Image Correlation Method (ICM) provides an accurate strain analysis by revealing strain concentrations and avoids damaging the tissue. The methodology has first been applied to human forehead skin and can be further expanded to other planar soft tissues. The failure characteristics for the skin in terms of ultimate stress are 3 MPa +/- 1.5 MPa. The ultimate global longitudinal strains are equal to 9.5%+/-1.9% (Green-Lagrange strain), which contrasts with the ultimate local longitudinal strain values of 24.0%+/-5.3% (Green-Lagrange strain). This difference is a consequence of the tissue heterogeneity, clearly illustrated by the heterogeneous distribution of the local strain field. All data will assist in developing the tissue constitutive law that will be implemented in finite element models.

  13. Determination of Original Infection Source of H7N9 Avian Influenza by Dynamical Model

    Science.gov (United States)

    Zhang, Juan; Jin, Zhen; Sun, Gui-Quan; Sun, Xiang-Dong; Wang, You-Ming; Huang, Baoxu

    2014-05-01

    H7N9, a newly emerging virus in China, travels among poultry and human. Although H7N9 has not aroused massive outbreaks, recurrence in the second half of 2013 makes it essential to control the spread. It is believed that the most effective control measure is to locate the original infection source and cut off the source of infection from human. However, the original infection source and the internal transmission mechanism of the new virus are not totally clear. In order to determine the original infection source of H7N9, we establish a dynamical model with migratory bird, resident bird, domestic poultry and human population, and view migratory bird, resident bird, domestic poultry as original infection source respectively to fit the true dynamics during the 2013 pandemic. By comparing the date fitting results and corresponding Akaike Information Criterion (AIC) values, we conclude that migrant birds are most likely the original infection source. In addition, we obtain the basic reproduction number in poultry and carry out sensitivity analysis of some parameters.

  14. Dynamic light scattering and atomic force microscopy techniques for size determination of polyurethane nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Giehl Zanetti-Ramos, Betina [Laboratorio de Bioenergetica e Bioquimica de Macromoleculas, Departamento de Ciencias Farmaceuticas (Brazil)], E-mail: betinagzramos@pq.cnpq.br; Beddin Fritzen-Garcia, Mauricia [Laboratorio de Bioenergetica e Bioquimica de Macromoleculas, Departamento de Ciencias Farmaceuticas (Brazil); Schweitzer de Oliveira, Cristian; Avelino Pasa, Andre [Laboratorio de Filmes Finos e Superficie, Departamento de Fisica (Brazil); Soldi, Valdir [Grupo de Estudos em Materiais Polimericos, Departamento de Quimica, Universidade Federal de Santa Catarina, 88040-900, Florianopolis, SC (Brazil); Borsali, Redouane [Centre de Recherche sur les Macromolecules Vegetales CERMAV/CNRS, 38041 - Grenoble (France); Creczynski-Pasa, Tania Beatriz [Laboratorio de Bioenergetica e Bioquimica de Macromoleculas, Departamento de Ciencias Farmaceuticas (Brazil)

    2009-03-01

    Nanoparticles have applications in various industrial fields principally in drug delivery. Nowadays, there are several processes for manufacturing colloidal polymeric systems and methods of preparation as well as of characterization. In this work, Dynamic Light Scattering and Atomic Force Microscopy techniques were used to characterize polyurethane nanoparticles. The nanoparticles were prepared by miniemulsion technique. The lipophilic monomers, isophorone diisocyanate (IPDI) and natural triol, were emulsified in water containing surfactant. In some formulations the poly(ethylene glycol) was used as co-monomer to obtain the hydrophilic and pegylated nanoparticles. Polyurethane nanoparticles observed by atomic force microscopy (AFM) were spherical with diameter around 209 nm for nanoparticles prepared without PEG. From AFM imaging two populations of nanoparticles were observed in the formulation prepared with PEG (218 and 127 nm) while dynamic light scattering (DLS) measurements showed a monodisperse size distribution around 250 nm of diameters for both formulations. The polydispersity index of the formulations and the experimental procedures could influence the particle size determination with these techniques.

  15. Inquiring the niche determinants of social media websites in dynamically mobile hypercompetitive communication era

    Directory of Open Access Journals (Sweden)

    Chih-Cheng Huang

    2016-03-01

    Full Text Available This research cross-employs the information communication distribution transaction and analytic network process models to effectively institute the hierarchical evaluated model and utilizes, in specific, fuzzy theory and the grey relation analysis approaches of multiple criteria decision-making methodology into the weight measurements of expert’s questionnaires from three analytical perspectives (user’s satisfaction, corporate commitment, and social trust of relationship quality in order to explore the niche determinants of the social media websites in the contemporarily hypercompetitive and dynamic online era. Consequently, as for the measured consequences after a series of complicated and systematical calculations, the most valuable findings in this research are (1 the technological interfaces of social media websites is a positive niche in the dynamically mobile hypercompetitive communication era and (2 the “social media websites” is in a position of becoming one of the social media mainstreams in the online technology field based on the measured weights from the detailed survey data collected from experts in this research.

  16. High frequency dynamics of BMG determined by synchrotron radiation: A microscopic picture

    Energy Technology Data Exchange (ETDEWEB)

    Serrano, Jorge, E-mail: jserrano@fa.upc.ed [Institucio Catalana de Recerca i Estudis Avancats (ICREA), Univ. Politecnica de Catalunya, Avda. del Canal Olimpic 15, Castelldefels (Spain); Dept. de Fisica Aplicada, EPSC, Univ. Politecnica de Catalunya, Avda. del Canal Olimpic 15, 08860 Castelldefels (Spain); Pineda, Eloi [Dept. de Fisica i Enginyeria Nuclear, ESAB, Univ. Politecnica de Catalunya, Avda. del Canal Olimpic 15, 08860 Castelldefels (Spain); Bruna, Pere [Dept. de Fisica Aplicada, EPSC, Univ. Politecnica de Catalunya, Avda. del Canal Olimpic 15, 08860 Castelldefels (Spain); Labrador, Ana [LLS, BM16-ESRF, BP 220, 38043 Grenoble Cedex 9 (France); Le Tacon, Mathieu; Krisch, Michael; Monaco, Giulio [European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, BP 220, 38043 Grenoble Cedex 9 (France); Crespo, Daniel [Dept. de Fisica Aplicada, EPSC, Univ. Politecnica de Catalunya, Avda. del Canal Olimpic 15, 08860 Castelldefels (Spain)

    2010-04-16

    Mechanical properties are becoming the focus in research on bulk metallic glasses (BMG), as they are the limiting factor for structural applications. A wide range of experimental techniques gives complementary macroscopic data that are often difficult to correlate with the microscopic structural knowledge of the same materials. Recently, high resolution inelastic X-ray scattering (IXS) was applied to determine the high frequency dynamics of BMG [T. Scopigno, J.-B. Suck, R. Angelini, F. Albergamo, G. Ruocco, Phys. Rev. Lett. 96 (2006) 135501]. This technique offers a new approach to the mechanic properties helping to bridge the gap between the microscopic and the macroscopic picture. Here we will present results of IXS experiments on bulk metallic glasses with different fragility values, obtained at the European Synchrotron Radiation Facility (ESRF) in Grenoble (France).

  17. System Dynamics Modeling for Determining Optimal Ship Sizes and Types in Coastal Liner Services

    Directory of Open Access Journals (Sweden)

    Sung-il Park

    2014-04-01

    Full Text Available The problem of determining the required ship investment for deployment is an ongoing problem faced by governments and ship operators. The nature of ship investment is capital-intensive and the return on investment is often take long time. This paper attempts to establish system dynamics modeling (SDM to simulate and solve this problem in order to help ship operators make effective strategic decisions. A case study of coastal liner services between Incheon and Baengnyeong Island in South Korea was performed. Using scenario analysis, the possible ship sizes (small: 350 tons; large: 2,500 tons and types (new or used were considered by comparing potential revenue with costs. The results indicated that putting a used large-sized ship into operation would accommodate the increasing passenger and cargo volumes, and improve customer services.

  18. Coupling of cytoplasm and adhesion dynamics determines cell polarization and locomotion

    CERN Document Server

    Bock, Martin; Möhl, Christoph

    2009-01-01

    Observations of single epidermal cells on flat adhesive substrates have revealed two distinct morphological and functional states, namely a non-migrating symmetric unpolarized state and a migrating asymmetric polarized state. These states are characterized by different spatial distributions and dynamics of important biochemical cell components: F-actin and myosin-II form the contractile part of the cytoskeleton, and integrin receptors in the plasma membrane connect F-actin filaments to the substratum. In this way, focal adhesion complexes are assembled, which determine cytoskeletal force transduction and subsequent cell locomotion. So far, physical models have reduced this phenomenon either to gradients in regulatory control molecules or to different mechanics of the actin filament system in different regions of the cell. Here we offer an alternative and self-organizational model incorporating polymerization, pushing and sliding of filaments, as well as formation of adhesion sites and their force dependent ki...

  19. 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.)

  20. 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...

  1. Molecular determinants of epidermal growth factor binding: a molecular dynamics study.

    Directory of Open Access Journals (Sweden)

    Jeffrey M Sanders

    Full Text Available The epidermal growth factor receptor (EGFR is a member of the receptor tyrosine kinase family that plays a role in multiple cellular processes. Activation of EGFR requires binding of a ligand on the extracellular domain to promote conformational changes leading to dimerization and transphosphorylation of intracellular kinase domains. Seven ligands are known to bind EGFR with affinities ranging from sub-nanomolar to near micromolar dissociation constants. In the case of EGFR, distinct conformational states assumed upon binding a ligand is thought to be a determining factor in activation of a downstream signaling network. Previous biochemical studies suggest the existence of both low affinity and high affinity EGFR ligands. While these studies have identified functional effects of ligand binding, high-resolution structural data are lacking. To gain a better understanding of the molecular basis of EGFR binding affinities, we docked each EGFR ligand to the putative active state extracellular domain dimer and 25.0 ns molecular dynamics simulations were performed. MM-PBSA/GBSA are efficient computational approaches to approximate free energies of protein-protein interactions and decompose the free energy at the amino acid level. We applied these methods to the last 6.0 ns of each ligand-receptor simulation. MM-PBSA calculations were able to successfully rank all seven of the EGFR ligands based on the two affinity classes: EGF>HB-EGF>TGF-α>BTC>EPR>EPG>AR. Results from energy decomposition identified several interactions that are common among binding ligands. These findings reveal that while several residues are conserved among the EGFR ligand family, no single set of residues determines the affinity class. Instead we found heterogeneous sets of interactions that were driven primarily by electrostatic and Van der Waals forces. These results not only illustrate the complexity of EGFR dynamics but also pave the way for structure-based design of

  2. Preparation of a 6-OH quaternized chitosan derivative through click reaction and its application to novel thermally induced/polyelectrolyte complex hydrogels.

    Science.gov (United States)

    Chen, Yu; Wang, Fengju; Zhang, Na; Li, Yi; Cheng, Bin; Zheng, Yongfa

    2017-07-11

    In the present study, a chitosan derivative with long chain quaternary ammonium locating grafted at 6-OH (CTS-6-QAS) was designed and prepared via a novel click reaction. The structure and thermal stability of the products of each step were determined with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Rheological tests indicate that CTS-6-QAS possesses excellent thermally induced hydrogel formation property in the presence of β-glycerophosphate (β-GP). Based on these results, a novel thermally induced/polyelectrolyte complex CTS-6-QAS/alginate (SA)/β-GP dual-network hydrogel was designed. This controllable preparation method can avoid the disadvantages of the preparation methods for single thermo-induced hydrogels and polyelectrolyte complex hydrogels, and promote the homogeneity of the hydrogel. Porous sponges were prepared by freeze-drying the CTS-6-QASSA/β-GP hydrogels. The effects of hydrogel preparation conditions on the porous structure and swelling property of the sponges were quantitatively investigated. Tea tree oil (TTO), a natural antibacterial agent, was successfully embedded in the hydrogel due to the lipophilicity of the long chain quaternary ammonium grafted at 6-OH of chitosan. The sustained release of TTO from the hydrogel was studied. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Application of Vehicle Dynamic Modeling in Uavs for Precise Determination of Exterior Orientation

    Science.gov (United States)

    Khaghani, M.; Skaloud, J.

    2016-06-01

    Advances in unmanned aerial vehicles (UAV) and especially micro aerial vehicle (MAV) technology together with increasing quality and decreasing price of imaging devices have resulted in growing use of MAVs in photogrammetry. The practicality of MAV mapping is seriously enhanced with the ability to determine parameters of exterior orientation (EO) with sufficient accuracy, in both absolute and relative senses (change of attitude between successive images). While differential carrier phase GNSS satisfies cm-level positioning accuracy, precise attitude determination is essential for both direct sensor orientation (DiSO) and integrated sensor orientation (ISO) in corridor mapping or in block configuration imaging over surfaces with low texture. Limited cost, size, and weight of MAVs represent limitations on quality of onboard navigation sensors and puts emphasis on exploiting full capacity of available resources. Typically short flying times (10-30 minutes) also limit the possibility of estimating and/or correcting factors such as sensor misalignment and poor attitude initialization of inertial navigation system (INS). This research aims at increasing the accuracy of attitude determination in both absolute and relative senses with no extra sensors onboard. In comparison to classical INS/GNSS setup, novel approach is presented here to integrated state estimation, in which vehicle dynamic model (VDM) is used as the main process model. Such system benefits from available information from autopilot and physical properties of the platform in enhancing performance of determination of trajectory and parameters of exterior orientation consequently. The navigation system employs a differential carrier phase GNSS receiver and a micro electro-mechanical system (MEMS) grade inertial measurement unit (IMU), together with MAV control input from autopilot. Monte-Carlo simulation has been performed on trajectories for typical corridor mapping and block imaging. Results reveal

  4. 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.

  5. 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

  6. An independent determination of Fomalhaut b's orbit and the dynamical effects on the outer dust belt

    CERN Document Server

    Beust, Hervé; Bonsor, Amy; Graham, J; Kalas, Paul; Lebreton, J; Lagrange, Anne-Marie; Ertel, Steve; Faramaz, Virginie; Thebault, Philippe

    2013-01-01

    The nearby star Fomalhaut harbours a cold, moderately eccentric dust belt with a sharp inner edge near 133 au. A low-mass, common proper motion companion (Fom b), was discovered near the inner edge and was identified as a planet candidate that could account for the belt morphology. However, the most recent orbit determination based on four epochs of astrometry over eight years reveals a highly eccentric orbit that appears to cross the belt in the sky plane projection. We perform here a full orbital determination based on the available astrometric data to independently validate the orbit estimates previously presented. Adopting our values for the orbital elements and their associated uncertainties, we then study the dynamical interaction between the planet and the dust ring, to check whether the proposed disk sculpting scenario by Fom b is plausible. We used a dedicated MCMC code to derive the statistical distributions of the orbital elements of Fom b. Then we used symplectic N-body integration to investigate ...

  7. Temporal dynamics and determinants of whole brain tissue volume changes during recovery from alcohol dependence.

    Science.gov (United States)

    Gazdzinski, Stefan; Durazzo, Timothy C; Meyerhoff, Dieter J

    2005-06-01

    Brain shrinkage and its partial reversibility with abstinence is a common neuroimaging finding in alcohol dependent individuals. We used an automated three-dimensional whole brain magnetic resonance imaging method (boundary shift integral) in 23 alcohol dependent individuals to measure the temporal dynamics of cerebral tissue and spinal fluid volume changes over a 12-month interval and to examine the major determinants of brain tissue change rates during abstinence and non-abstinence. We found more rapid brain tissue gain during the first month of sobriety than in the following months. The most rapid volume recovery was observed in abstinent individuals with the greatest baseline brain shrinkage and drinking severity. The rapid reversal of brain volume gains in non-abstinent individuals and tissue volume changes are modulated by duration of abstinence and non-abstinence periods, as well as recency of non-abstinence. Age, family history density of alcoholism, relapse severity, and duration or age of onset of heavy drinking were not major determinants of brain shrinkage and brain volume recovery rates. Treatment providers may use this tangible information to reinforce the biomedical benefits of sobriety. Previous quantitative measurements of brain volumes in alcohol dependent individuals performed after several weeks of abstinence likely underestimated the full extent of chronic alcohol-associated brain shrinkage.

  8. Using Maximal Isometric Force to Determine the Optimal Load for Measuring Dynamic Muscle Power

    Science.gov (United States)

    Spiering, Barry A.; Lee, Stuart M. C.; Mulavara, Ajitkumar P.; Bentley, Jason R.; Nash, Roxanne E.; Sinka, Joseph; Bloomberg, Jacob J.

    2009-01-01

    Maximal power output occurs when subjects perform ballistic exercises using loads of 30-50% of one-repetition maximum (1-RM). However, performing 1-RM testing prior to power measurement requires considerable time, especially when testing involves multiple exercises. Maximal isometric force (MIF), which requires substantially less time to measure than 1-RM, might be an acceptable alternative for determining the optimal load for power testing. PURPOSE: To determine the optimal load based on MIF for maximizing dynamic power output during leg press and bench press exercises. METHODS: Twenty healthy volunteers (12 men and 8 women; mean +/- SD age: 31+/-6 y; body mass: 72 +/- 15 kg) performed isometric leg press and bench press movements, during which MIF was measured using force plates. Subsequently, subjects performed ballistic leg press and bench press exercises using loads corresponding to 20%, 30%, 40%, 50%, and 60% of MIF presented in randomized order. Maximal instantaneous power was calculated during the ballistic exercise tests using force plates and position transducers. Repeated-measures ANOVA and Fisher LSD post hoc tests were used to determine the load(s) that elicited maximal power output. RESULTS: For the leg press power test, six subjects were unable to be tested at 20% and 30% MIF because these loads were less than the lightest possible load (i.e., the weight of the unloaded leg press sled assembly [31.4 kg]). For the bench press power test, five subjects were unable to be tested at 20% MIF because these loads were less than the weight of the unloaded aluminum bar (i.e., 11.4 kg). Therefore, these loads were excluded from analysis. A trend (p = 0.07) for a main effect of load existed for the leg press exercise, indicating that the 40% MIF load tended to elicit greater power output than the 60% MIF load (effect size = 0.38). A significant (p . 0.05) main effect of load existed for the bench press exercise; post hoc analysis indicated that the effect of

  9. 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.

  10. 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.

  11. On higher ground: how well can dynamic body acceleration determine speed in variable terrain?

    Directory of Open Access Journals (Sweden)

    Owen R Bidder

    Full Text Available INTRODUCTION: Animal travel speed is an ecologically significant parameter, with implications for the study of energetics and animal behaviour. It is also necessary for the calculation of animal paths by dead-reckoning. Dead-reckoning uses heading and speed to calculate an animal's path through its environment on a fine scale. It is often used in aquatic environments, where transmission telemetry is difficult. However, its adoption for tracking terrestrial animals is limited by our ability to measure speed accurately on a fine scale. Recently, tri-axial accelerometers have shown promise for estimating speed, but their accuracy appears affected by changes in substrate and surface gradients. The purpose of the present study was to evaluate four metrics of acceleration; Overall dynamic body acceleration (ODBA, vectorial dynamic body acceleration (VDBA, acceleration peak frequency and acceleration peak amplitude, as proxies for speed over hard, soft and inclined surfaces, using humans as a model species. RESULTS: A general linear model (GLM showed a significant difference in the relationships between the metrics and speed depending on substrate or surface gradient. When the data from all surface types were considered together, VeDBA had the highest coefficient of determination. CONCLUSIONS: All of the metrics showed some variation in their relationship with speed according to the surface type. This indicates that changes in the substrate or surface gradient during locomotion by animals would produce errors in speed estimates, and also in dead-reckoned tracks if they were calculated from speeds based entirely on a priori calibrations. However, we describe a method by which the relationship between acceleration metrics and speed can be corrected ad hoc, until tracks accord with periodic ground truthed positions, obtained via a secondary means (e.g. VHF or GPS telemetry. In this way, dead-reckoning provides a means to obtain fine scale movement data

  12. Simple method of dynamic Young’s modulus determination in lime and cement mortars

    Directory of Open Access Journals (Sweden)

    Rosell, J. R.

    2011-03-01

    Full Text Available The present work explains a simple method to determine the dynamic Young module (MOE by inducing a set of small mechanical perturbation to samples of lime and cement mortars and correlating the results obtained with results determined using other techniques and methods. The procedure described herein follows the instructions stated in the UNE-EN ISO 12680-1 standard for refractory products although in this study the instructions are applied to standardized RILEM 4x4x16 cm test samples made of lime and cement mortars. In addition, MOE determinations are obtained by using ultrasonic impulse velocity while static Young's modulus determinations are obtained by performing conventional bending tests. The ability of this procedure to correlate with results from other techniques, along with its simplicity, suggests that it can be widely adapted to determine the deformability of mortars under load using standardized samples.

    El presente trabajo muestra un método simple para determinar el módulo de Young dinámico (MOE a partir de pequeñas perturbaciones mecánicas producidas a probetas de mortero de cal y de cemento, correlacionando los resultados obtenidos con las correspondientes mediciones realizadas con otras técnicas. El procedimiento sigue básicamente las instrucciones fijadas en la norma UNE-EN ISO 12680-1 de productos refractarios, pero aplicándolo a probetas normalizadas RILEM 4x4x16 de morteros confeccionados con cal y cemento. Paralelamente se realizan determinaciones del MOE a partir de la velocidad de paso de impulsos ultrasónicos y determinaciones del módulo de Young estático a partir de ensayos de flexión convencionales. La simplicidad del método aplicado y la correlación de los resultados obtenidos con las variables medidas permiten concluir que esta metodología es de aplicación directa para determinar la deformabilidad bajo carga de los morteros a partir de probetas normalizadas.

  13. Dynamic rupture simulation with an experimentally-determined friction law leads to slip-pulse propagation

    Science.gov (United States)

    Liao, Z.; Chang, J. C.; Reches, Z.

    2013-12-01

    We simulate the dynamic rupture along a vertical, strike-slip fault in an elastic half-space. The fault has frictional properties that were determined in high-velocity, rotary shear apparatus Sierra-White granite. The experimental fault was abruptly loaded by a massive flywheel, which is assumed to simulate the loading of a fault patch during an earthquake, and termed Earthquake-Like-Slip Event (ELSE) (Chang et al., 2012). The experiments revealed systematic alteration between slip-weakening and slip-strengthening (Fig. 1A), and were considered as proxies of fault-patch behavior during earthquakes of M = 4-8. We used the friction-distance relations of these experiments to form an empirical slip-dependent friction model, ELSE-model (Fig. 1B). For the dynamic rupture simulation, we used the program of Ampuero (2002) (2D spectral boundary integral elements) designed for anti-plane (mode III) shear fracturing. To compare with published works, the calculations used a crust with mechanical properties and stress state of Version 3 benchmark of SCEC (Harris et al., 2004). The calculations with a fault of ELSE-model friction revealed: (1) Rupture propagation in a slip-pulse style with slip cessation behind the pulse; (2) Systematic decrease of slip distance away from the nucleation zone; and (3) Spontaneous arrest of the dynamic rupture without a barrier. These features suggest a rupture of a self-healing slip-pulse mode (Fig. 1C), in contrast to rupturing of a fault with linear slip-weakening friction (Fig. 1B) (Rojas et al., 2008) in crack-like mode and no spontaneous arrest. We deduce that the slip-pulse in our simulation results from the fast recovery of shear strength as observed in ELSE experiments, and argue that incorporating this experimentally-based friction model to rupture modeling produces realistic propagation style of earthquake rupture. Figure 1 Fault patch behavior during an earthquake. (A) Experimental evolution of frictional stress, slip velocity, and

  14. Molecular Dynamics Simulations Illuminate the Role of Counterion Condensation in the Electrophoretic Transport of Homogalacturonans.

    Science.gov (United States)

    Irani, Amir H; Owen, Jessie L; Mercadante, Davide; Williams, Martin A K

    2017-02-13

    Homogalacturonans (HGs) are polysaccharide copolymers of galacturonic acid and its methylesterified counterpart. The inter- and intramolecular distributions of the methylesterifed residues are vital behavior-determining characteristics of a sample's structure, and much experimental effort has been directed to their measurement. While many techniques are able to measure the sample-averaged degree of methylesterification (DM), the measurement of inter- and intramolecular charge distributions are challenging. Here, molecular dynamics (MD) simulations are used to calculate the electrophoretic mobilities of HGs that have different amounts and distributions of charges placed along the backbone. The simulations are shown to capture experimental results well, even for low-DM samples that possess high charge densities. In addition, they illuminate the role that local counterion condensation can play in the determination of the electrophoretic mobility of heterogeneous blocky polyelectrolytes that cannot be adequately described by a single chain-averaged charge spacing.

  15. 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.

  16. 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.

  17. 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.

  18. 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) ).

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

    Science.gov (United States)

    Sanyal, Oishi

    Polyelectrolyte multilayer (PEM) membranes present a special class of nanostructured membranes which have potential applications in a variety of water treatment operations. These membranes are fabricated by the layer-by-layer (LbL) assembly of alternately charged polyelectrolytes on commercial membrane surfaces. A large variety of polyelectrolytes and their varied deposition conditions (pH, number of bilayers etc.) allow very fine tuning of the membrane performance in terms of permeability and rejection. The first part of this thesis is about the application of PEM membranes to the removal of perchlorate ion from water. Being a monovalent ion, it is most effectively removed by a reverse osmosis (RO) membrane. However, these membranes inherently have very low fluxes which lead to high pressure requirements. In our work, we modified the surface of a nanofiltration (NF) membrane by the LbL assembly of oppositely charged polyelectrolytes. The appropriate tuning of the LbL conditions led to the development of a membrane with significantly higher flux than RO membranes but with equivalent perchlorate rejection. This was one of the best trade-offs offered by PEM membranes for monovalent ion rejection as has been reported in literature so far. While PEM membranes have mostly shown great potential in ion-rejection studies, they have seldom been tested for real wastewater effluents. The second part of this thesis, therefore, deals with evaluating the applicability of PEM membranes to treating an electrocoagulation (EC)-treated high strength wastewater. Two types of very commonly used polyelectrolyte combinations were tried out -- one of which was an ionically crosslinked system and the other one was covalently crosslinked. Both the types of PEM membranes showed a high level of COD reduction from the feed stream with higher fluxes than commercial RO membranes. One major challenge in using membranes for wastewater treatment is their fouling propensity. Like many other

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Determination of Activation Energy of Relaxation Events in Composite Solid Propellants by Dynamic Mechanical Analysis

    Directory of Open Access Journals (Sweden)

    B. K Bihari

    2014-03-01

    Full Text Available The shelf life of a composite solid propellant is one of the critical aspects for the usage of solid propellants. To assess the ageing behavior of the composite solid propellant, the activation energy is a key parameter. The activation energy is determined by analysis of visco-elastic response of the composite solid propellant when subjected to sinusoidal excitation. In the present study, dynamic mechanical analyzer was used to characterize six different types of propellants based on hydroxyl terminated polybutadiene, aluminium, ammonium perchlorate cured with toluene diisocyanate having burning rates varying from 5 mm/s to 25 mm/s at 7000 kPa. Each propellant sample was given a multi-frequency strain of 0.01 percent at three discrete frequencies (3.5 Hz, 11 Hz, 35 Hz in the temperature range -80 °C to + 80 °C. It was observed that all the propellants have shown two relaxation events (α- and β- transition in the temperature range -80 °C to +80 °C. The α-transition was observed between -66 °C and -51 °C and β-transition between 7 °C and 44 °C for the propellants studied. The activation energy for both transitions was determined by Arrhenius plot from dynamic properties measured at different frequencies and also by time temperature superposition principle using Williams-Landel-Ferry and Arrhenius temperature dependence equations. The data reveal that the activation energy corresponding to α-transition varies from 90 kJ/mol to 125 kJ/mol for R-value between 0.7 to 0.9 while for β-transition the values are from 75 kJ/mol to 92 kJ/mol. The activation energy corresponding to β-transition may be used to predict the useful life of solid propellant.Defence Science Journal, 2014, 64(2, pp. 173-178. DOI: http://dx.doi.org/10.14429/dsj.64.3818

  6. 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 ...

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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).

  1. 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.

  2. Phase equilibrium calculations of ternary liquid mixtures with binary interaction parameters and molecular size parameters determined from molecular dynamics.

    Science.gov (United States)

    Oh, Suk Yung; Bae, Young Chan

    2010-07-15

    The method presented in this paper was developed to predict liquid-liquid equilibria in ternary liquid mixtures by using a combination of a thermodynamic model and molecular dynamics simulations. In general, common classical thermodynamic models have many parameters which are determined by fitting a model with experimental data. This proposed method, however, provides a simple procedure for calculating liquid-liquid equilibria utilizing binary interaction parameters and molecular size parameters determined from molecular dynamics simulations. This method was applied to mixtures containing water, hydrocarbons, alcohols, chlorides, ketones, acids, and other organic liquids over various temperature ranges. The predicted results agree well with the experimental data without the use of adjustable parameters.

  3. Motivational dynamics of eating regulation: a self-determination theory perspective.

    Science.gov (United States)

    Verstuyf, Joke; Patrick, Heather; Vansteenkiste, Maarten; Teixeira, Pedro J

    2012-03-02

    Within Western society, many people have difficulties adequately regulating their eating behaviors and weight. Although the literature on eating regulation is vast, little attention has been given to motivational dynamics involved in eating regulation. Grounded in Self-Determination Theory (SDT), the present contribution aims to provide a motivational perspective on eating regulation. The role of satisfaction and thwarting of the basic psychological needs for autonomy, competence, and relatedness is introduced as a mechanism to (a) explain the etiology of body image concerns and disordered eating and (b) understand the optimal regulation of ongoing eating behavior for healthy weight maintenance. An overview of empirical studies on these two research lines is provided. In a final section, the potential relevance and value of SDT in relation to prevailing theoretical models in the domain of eating regulation is discussed. Although research on SDT in the domain of eating regulation is still in its early stages and more research is clearly needed, this review suggests that the SDT represents a promising framework to more thoroughly study and understand the motivational processes involved in eating regulation and associated problems.

  4. Determination of thermal properties pure ThO2 using classical molecular dynamics simulations

    Science.gov (United States)

    Ghosh, Partha S.; Kaur, Karamvir; Ali, K.; Arya, A.; Dey, G. K.

    2016-05-01

    This paper calculates lattice thermal expansion (LTE), thermal conductivity (TC) and melting temperature (MT) of ThO2 using classical molecular dynamic simulations. In this study we consider two set of interatomic potential consisting of Coulomb-Buckingham (Buck) and Coulomb-Buckingham-Morse-Many body (BMM) potential form. The MD calculated LTE of 10.29 × 10-6 and 10.61 × 10-6 K-1 using BMM and Buck potential, respectively, is slightly higher than the experimentally determined values (9.54 - 9.86 × 10-6 K-1). The MD calculated TC values in the high temperature range (600 to 1200 K) accords very well with the experimental measurements and at the low temperature range (300-500 K) our results are slightly different from experimental results as our presumption that the dominant mechanism for phonon scattering is the Umklapp process. The MD calculated MT of ThO2 using Buck and BMM potential model is 3662.5±12.5 K and 3812.5±12.5 K, respectively, and these values are in reasonable agreement with previous experimental values.

  5. Transcription closed and open complex dynamics studies reveal balance between genetic determinants and co-factors.

    Science.gov (United States)

    Sala, Adrien; Shoaib, Muhammad; Anufrieva, Olga; Mutharasu, Gnanavel; Jahan Hoque, Rawnak; Yli-Harja, Olli; Kandhavelu, Meenakshisundaram

    2015-05-19

    In E. coli, promoter closed and open complexes are key steps in transcription initiation, where magnesium-dependent RNA polymerase catalyzes RNA synthesis. However, the exact mechanism of initiation remains to be fully elucidated. Here, using single mRNA detection and dual reporter studies, we show that increased intracellular magnesium concentration affects Plac initiation complex formation resulting in a highly dynamic process over the cell growth phases. Mg2+ regulates transcription transition, which modulates bimodality of mRNA distribution in the exponential phase. We reveal that Mg2+ regulates the size and frequency of the mRNA burst by changing the open complex duration. Moreover, increasing magnesium concentration leads to higher intrinsic and extrinsic noise in the exponential phase. RNAP-Mg2+ interaction simulation reveals critical movements creating a shorter contact distance between aspartic acid residues and Nucleotide Triphosphate residues and increasing electrostatic charges in the active site. Our findings provide unique biophysical insights into the balanced mechanism of genetic determinants and magnesium ion in transcription initiation regulation during cell growth.

  6. Absolute densities, masses, and radii of the WASP-47 system determined dynamically

    CERN Document Server

    Almenara, J M; Bonfils, X; Udry, S

    2016-01-01

    We present a self-consistent modelling of the available light curve and radial velocity data of WASP-47 that takes into account the gravitational interactions between all known bodies in the system. The joint analysis of light curve and radial velocity data in a multi-planetary system allows deriving absolute densities, radii, and masses without the use of theoretical stellar models. For WASP-47 the precision is limited by the reduced dynamical information that is due to the short time span of the K2 light curve. We achieve a precision of around 22% for the radii of the star and the transiting planets, between 40% and 60% for their masses, and between 1.5% and 38% for their densities. All values agree with previously reported measurements. When theoretical stellar models are included, the system parameters are determined with a precision that exceeds that achieved by previous studies, thanks to the self-consistent modelling of light curve and radial velocity data.

  7. Vortices determine the dynamics of biodiversity in cyclical interactions with protection spillovers

    CERN Document Server

    Szolnoki, Attila

    2015-01-01

    If rock beats scissors and scissors beat paper, one might assume that rock beats paper too. But this is not the case for intransitive relationships that make up the famous rock-paper-scissors game. However, the sole presence of paper might prevent rock from beating scissors, simply because paper beats rock. This is the blueprint for the rock-paper-scissors game with protection spillovers, which has recently been introduced as a new paradigm for biodiversity in well-mixed microbial populations. Here we study the game in structured populations, demonstrating that protection spillovers give rise to spatial patterns that are impossible to observe in the classical rock-paper-scissors game. We show that the spatiotemporal dynamics of the system is determined by the density of stable vortices, which may ultimately transform to frozen states, to propagating waves, or to target waves with reversed propagation direction, depending further on the degree and type of randomness in the interactions among the species. If vo...

  8. Absolute densities, masses, and radii of the WASP-47 system determined dynamically

    Science.gov (United States)

    Almenara, J. M.; Díaz, R. F.; Bonfils, X.; Udry, S.

    2016-10-01

    We present a self-consistent modelling of the available light curve and radial velocity data of WASP-47 that takes into account the gravitational interactions between all known bodies in the system. The joint analysis of light curve and radial velocity data in a multi-planetary system allows deriving absolute densities, radii, and masses without the use of theoretical stellar models. For WASP-47 the precision is limited by the reduced dynamical information that is due to the short time span of the K2 light curve. We achieve a precision of around 22% for the radii of the star and the transiting planets, between 40% and 60% for their masses, and between 1.5% and 38% for their densities. All values agree with previously reported measurements. When theoretical stellar models are included, the system parameters are determined with a precision that exceeds that achieved by previous studies, thanks to the self-consistent modelling of light curve and radial velocity data.

  9. Motivational dynamics of eating regulation: a self-determination theory perspective

    Directory of Open Access Journals (Sweden)

    Verstuyf Joke

    2012-03-01

    Full Text Available Abstract Within Western society, many people have difficulties adequately regulating their eating behaviors and weight. Although the literature on eating regulation is vast, little attention has been given to motivational dynamics involved in eating regulation. Grounded in Self-Determination Theory (SDT, the present contribution aims to provide a motivational perspective on eating regulation. The role of satisfaction and thwarting of the basic psychological needs for autonomy, competence, and relatedness is introduced as a mechanism to (a explain the etiology of body image concerns and disordered eating and (b understand the optimal regulation of ongoing eating behavior for healthy weight maintenance. An overview of empirical studies on these two research lines is provided. In a final section, the potential relevance and value of SDT in relation to prevailing theoretical models in the domain of eating regulation is discussed. Although research on SDT in the domain of eating regulation is still in its early stages and more research is clearly needed, this review suggests that the SDT represents a promising framework to more thoroughly study and understand the motivational processes involved in eating regulation and associated problems.

  10. Towards determining appropriate hydrodynamic conditions for in vitro in vivo correlations using computational fluid dynamics.

    Science.gov (United States)

    D'Arcy, Deirdre M; Healy, Anne Marie; Corrigan, Owen I

    2009-06-28

    One of the earliest level A in vitro dissolution in vivo absorption correlations (IVIVCs) was established by Levy and co-workers in 1965 using a beaker dissolution apparatus Levy et al., 1965. In the current work, the computational fluid dynamics (CFD) package, Fluent((R)), was used to simulate the hydrodynamics within the Levy beaker apparatus and compare them to those within the paddle and basket apparatuses. In vitro velocity values relevant to in vivo dissolution, presented as apparent gastrointestinal fluid velocity (AGV) values, were calculated. The AGV values were estimated from IVIVCs of immediate release (IR) dosage forms in each apparatus and CFD simulations. The simulations from the Levy apparatus revealed complex hydrodynamics in the region of the stirrer blades, and radial inflow at the centre of the beaker base. The calculated AGV values ranged from 0.001 to 0.026ms(-1). In vitro fluid velocities should reflect in vivo dissolution rates affected by natural convection and gastrointestinal motility, in addition to local fluid velocity. The maximum CFD generated velocity at the base of the paddle apparatus at 20rpm was similar to the average maximum AGV value determined, suggesting use of agitation rates which are lower than those commonly used (e.g. 50rpm in the paddle apparatus) may be appropriate when attempting an IVIVC for IR dosage forms.

  11. Determination of benzene residues in recycled polyethylene terephthalate (PETE) by dynamic headspace-gas chromatography.

    Science.gov (United States)

    Komolprasert, V; Hargraves, W A; Armstrong, D J

    1994-01-01

    A dynamic headspace-gas chromatography (HS/GC) method was developed to quantitate benzene in recycled PETE material derived from 21 PETE beverage bottles. The analytical system consisted of a purge-and-trap apparatus which was interfaced directly with a gas chromatograph/flame ionization detector. Cryofocusing and non-cryofocusing GC systems were used. The technique was applied to spiked PETE test samples which were prepared at various benzene concentrations ranging from 100 ppb to 117 ppm. The initial spiked benzene concentration in the PETE test samples was determined gravimetrically. The HS/GC technique was limited by the slow desorption rate of benzene from the PETE matrix; as a result, multipurges were performed at 60 degrees C. Regression analysis was done on the multipurge data to develop a desorption model which would predict the total amount of benzene in the PETE. The calculated results agreed with the experimental recoveries within +/- 10%. Recovery depended on the initial benzene level in the PETE and ranged from 70 to 90% after the first five purges.

  12. Determination of the Optimal Fourier Number on the Dynamic Thermal Transmission

    Science.gov (United States)

    Bruzgevičius, P.; Burlingis, A.; Norvaišienė, R.

    2016-12-01

    This article represents the result of experimental research on transient heat transfer in a multilayered (heterogeneous) wall. Our non-steady thermal transmission simulation is based on a finite-difference calculation method. The value of a Fourier number shows the similarity of thermal variation in conditional layers of an enclosure. Most scientists recommend using no more than a value of 0.5 for the Fourier number when performing calculations on dynamic (transient) heat transfer. The value of the Fourier number is determined in order to acquire reliable calculation results with optimal accuracy. To compare the results of simulation with experimental research, a transient heat transfer calculation spreadsheet was created. Our research has shown that a Fourier number of around 0.5 or even 0.32 is not sufficient ({≈ }17 % of oscillation amplitude) for calculations of transient heat transfer in a multilayered wall. The least distorted calculation results were obtained when the multilayered enclosure was divided into conditional layers with almost equal Fourier number values and when the value of the Fourier number was around 1/6, i.e., approximately 0.17. Statistical deviation analysis using the Statistical Analysis System was applied to assess the accuracy of the spreadsheet calculation and was developed on the basis of our established methodology. The mean and median absolute error as well as their confidence intervals has been estimated by the two methods with optimal accuracy ({F}_{oMDF}= 0.177 and F_{oEPS}= 0.1633 values).

  13. Determination of Consumer Behaviour Dynamics Relating to Food Products: “Trakya Region Example”

    Directory of Open Access Journals (Sweden)

    I.H. Inan

    2009-01-01

    Full Text Available In this study, it has been determined the dynamics of consumer behaviours of individuals who live in rural and urban areas concerning food products and it analyses the effective factors on consumers food consumption choice in families, based in Trakya Region (Tekirdag, Edirne, Kırklareli. The study was conducted with a total of 770 households 385 people in towns and 385 people in rural areas, 770 people in total of which 385 was from rural areas, and 385 from urban areas.The effective factors on consumer behaviour when purchasing food products have been evaluated by Multivariate Analysis of Variance (MANOVA and T-Test and Factor Analysis Methods in rural and urban areas in Trakya Region.This study indicates that families who live in urban areas of Trakya Region give more importance to food consumption compared to the ones living in rural areas. Also families living in urban and rural areas are concerned about “the Foot-and-Mouth Disease Mad Cow (BSE and Avian Influenza”.

  14. TECHNIQUE FOR DETERMINATION OF SURFACE FRACTAL DIMENSION AND MORPHOLOGY OF MESOPOROUS TITANIA USING DYNAMIC FLOW ADSORPTION AND ITS CHARACTERIZATION

    OpenAIRE

    Tursiloadi, Silvester

    2010-01-01

    A technique to determine the surface fractal dimension of mesoporous TiO­2 using a dynamic flow adsorption instrument is described. Fractal dimension is an additional technique to characterize surface morphology. Surface fractal dimension, a quantitative measurement of surface ruggedness, can be determined by adsorbing a homologous series of adsorbates onto an adsorbent sample of mesoporous TiO­2. Titania wet gel prepared by hydrolysis of Ti-alkoxide was immersed in the flow of supercritical ...

  15. A ratiometric nanosensor based on conjugated polyelectrolyte-stabilized AgNPs for ultrasensitive fluorescent and colorimetric sensing of melamine.

    Science.gov (United States)

    Zhu, Xixi; Xiao, Yi; Jiang, Xiaoying; Li, Jiahui; Qin, Hongling; Huang, Hongmei; Zhang, Youyu; He, Xiaoxiao; Wang, Kemin

    2016-05-01

    A new ratiometric nanosensor is developed for selective and ultrasensitive detection of melamine based on conjugated polyelectrolyte (CPE)-stabilized silver nanoparticles (P1-AgNPs) by perfectly combining the advantages of CPE and AgNPs. P1 featuring a π-delocalized backbone bearing pyridinyl groups can act as an excellent dual-emission fluorescent probe as well as a polymer localizer for AgNPs. In the presence of melamine, the fluorescence intensity at 386nm increases owing to the turn-on of the fluorescence of P1, whereas FL intensity at 488nm decreases due to the melamine-induced aggregation and subsequent aggregation-enhanced emission quenching of P1-AgNPs, therefore leading to the ratiometric fluorescent sensing of analyte. Moreover, analyte-induced aggregation of P1-AgNPs also allows the ratiometric colorimetric measurement of melamine. Under the optimum conditions, this facile ratiometric nanosensor favors the fluorescent and colorimetric determination of melamine in liquid milk products with the detection limit as low as 0.1 and 0.45nM, respectively.

  16. Some variables affecting the characteristics of Eudragit E-sodium alginate polyelectrolyte complex as a tablet matrix for diltiazem hydrochloride.

    Science.gov (United States)

    Yusif, Rehab Mohammad; Abu Hashim, Irhan Ibrahim; El-Dahan, Marwa Salah

    2014-03-01

    Eudragit E (EE)-sodium alginate (SA) polyelectrolyte complexes (PECs) were prepared at pH 4 and 5.8 using sodium alginate of high (SAH) and low viscosity (SAL). The optimum EE-SA complexation mass ratio was determined using viscosity measurements. Interactions between EE and SA in PECs were characterized by Fourier transform infra-red spectroscopy (FT-IR) and differential scanning calorimetry (DSC). Diltiazem hydrochloride (DTZ HCl) tablets were prepared using the prepared EE-SA PECs and their physical mixtures at different ratios as matrices. Tablets were evaluated for swelling characteristics and in vitro drug release. Tablets containing EE-SAH physical mixtures of ratios (1.5:1 and 1:3) as matrices were effective in achieving sustained release of DTZ HCl, where the percent drug released was significantly (p < 0.05) decreased compared to that from tablets either containing the same ratios of EE-SAL physical mixtures or the preformed EE- -SAH and EE-SAL PECs.

  17. Determination of the Orientation and Dynamics of Ergosterol in Model Membranes Using Uniform 13C Labeling and Dynamically Averaged 13C Chemical Shift Anisotropies as Experimental Restraints

    Science.gov (United States)

    Soubias, O.; Jolibois, F.; Massou, S.; Milon, A.; Réat, V.

    2005-01-01

    A new strategy was established to determine the average orientation and dynamics of ergosterol in dimyristoylphosphatidylcholine model membranes. It is based on the analysis of chemical shift anisotropies (CSAs) averaged by the molecular dynamics. Static 13C CSA tensors were computed by quantum chemistry, using the gauge-including atomic-orbital approach within Hartree-Fock theory. Uniformly 13C-labeled ergosterol was purified from Pichia pastoris cells grown on labeled methanol. After reconstitution into dimyristoylphosphatidylcholine lipids, the complete 1H and 13C assignment of ergosterol's resonances was performed using a combination of magic-angle spinning two-dimensional experiments. Dynamically averaged CSAs were determined by standard side-band intensity analysis for isolated 13C resonances (C3 and ethylenic carbons) and by off-magic-angle spinning experiments for other carbons. A set of 18 constraints was thus obtained, from which the sterol's molecular order parameter and average orientation could be precisely defined. The validity of using computed CSAs in this strategy was verified on cholesterol model systems. This new method allowed us to quantify ergosterol's dynamics at three molar ratios: 16 mol % (Ld phase), 30 mol % (Lo phase), and 23 mol % (mixed phases). Contrary to cholesterol, ergosterol's molecular diffusion axis makes an important angle (14°) with the inertial axis of the rigid four-ring system. PMID:15923221

  18. The Impact of the Gas Distribution on the Determination of Dynamical Masses of Galaxies Using Unresolved Observations

    NARCIS (Netherlands)

    de Blok, W. J. G.; Walter, Fabian

    2014-01-01

    Dynamical mass (M dyn) is a key property of any galaxy, yet a determination of M dyn is not straightforward if spatially resolved measurements are not available. This situation occurs in single-dish H I observations of the local universe, but also frequently in high-redshift observations. M dyn meas

  19. Viral and epidemiological determinants of the invasion dynamics of novel dengue genotypes.

    Directory of Open Access Journals (Sweden)

    José Lourenço

    Full Text Available BACKGROUND: Dengue has become a major concern for international public health. Frequent epidemic outbreaks are believed to be driven by a complex interplay of immunological interactions between its four co-circulating serotypes and large fluctuations in mosquito densities. Viral lineage replacement events, caused for example by different levels of cross-protection or differences in viral fitness, have also been linked to a temporary change in dengue epidemiology. A major replacement event was recently described for South-East Asia where the Asian-1 genotype of dengue serotype 2 replaced the resident Asian/American type. Although this was proposed to be due to increased viral fitness in terms of enhanced human-to-mosquito transmission, no major change in dengue epidemiology could be observed. METHODS/RESULTS: Here we investigate the invasion dynamics of a novel, advantageous dengue genotype within a model system and determine the factors influencing the success and rate of fixation as well as their epidemiological consequences. We find that while viral fitness overall correlates with invasion success and competitive exclusion of the resident genotype, the epidemiological landscape plays a more significant role for successful emergence. Novel genotypes can thus face high risks of stochastic extinction despite their fitness advantage if they get introduced during episodes of high dengue prevalence, especially with respect to that particular serotype. CONCLUSION: The rarity of markers for positive selection has often been explained by strong purifying selection whereby the constraints imposed by dengue's two-host cycle are expected to result in a high rate of deleterious mutations. Our results demonstrate that even highly beneficial mutants are under severe threat of extinction, which would suggest that apart from purifying selection, stochastic effects and genetic drift beyond seasonal bottlenecks are equally important in shaping dengue's viral

  20. Dynamics and molecular determinants of cytoplasmic lipid droplet clustering and dispersion.

    Directory of Open Access Journals (Sweden)

    David J Orlicky

    Full Text Available Perilipin-1 (Plin1, a prominent cytoplasmic lipid droplet (CLD binding phosphoprotein and key physiological regulator of triglyceride storage and lipolysis in adipocytes, is thought to regulate the fragmentation and dispersion of CLD that occurs in response to β-adrenergic activation of adenylate cyclase. Here we investigate the dynamics and molecular determinants of these processes using cell lines stably expressing recombinant forms of Plin1 and/or other members of the perilipin family. Plin1 and a C-terminal CLD-binding fragment of Plin1 (Plin1CT induced formation of single dense CLD clusters near the microtubule organizing center, whereas neither an N-terminal CLD-binding fragment of Plin1, nor Plin2 or Plin3 induced clustering. Clustered CLD coated by Plin1, or Plin1CT, dispersed in response to isoproterenol, or other agents that activate adenylate cyclase, in a process inhibited by the protein kinase A inhibitor, H89, and blocked by microtubule disruption. Isoproterenol-stimulated phosphorylation of CLD-associated Plin1 on serine 492 preceded their dispersion, and live cell imaging showed that cluster dispersion involved initial fragmentation of tight clusters into multiple smaller clusters, which then fragmented into well-dispersed individual CLD. siRNA knockdown of the cortical actin binding protein, moesin, induced disaggregation of tight clusters into multiple smaller clusters, and inhibited the reaggregation of dispersed CLD into tight clusters. Together these data suggest that the clustering and dispersion processes involve a complex orchestration of phosphorylation-dependent, microtubule-dependent and independent, and microfilament dependent steps.

  1. Dynamics and Molecular Determinants of Cytoplasmic Lipid Droplet Clustering and Dispersion

    Science.gov (United States)

    Stefanski, Adrianne L.; McManaman, James L.

    2013-01-01

    Perilipin-1 (Plin1), a prominent cytoplasmic lipid droplet (CLD) binding phosphoprotein and key physiological regulator of triglyceride storage and lipolysis in adipocytes, is thought to regulate the fragmentation and dispersion of CLD that occurs in response to β-adrenergic activation of adenylate cyclase. Here we investigate the dynamics and molecular determinants of these processes using cell lines stably expressing recombinant forms of Plin1 and/or other members of the perilipin family. Plin1 and a C-terminal CLD-binding fragment of Plin1 (Plin1CT) induced formation of single dense CLD clusters near the microtubule organizing center, whereas neither an N-terminal CLD-binding fragment of Plin1, nor Plin2 or Plin3 induced clustering. Clustered CLD coated by Plin1, or Plin1CT, dispersed in response to isoproterenol, or other agents that activate adenylate cyclase, in a process inhibited by the protein kinase A inhibitor, H89, and blocked by microtubule disruption. Isoproterenol-stimulated phosphorylation of CLD-associated Plin1 on serine 492 preceded their dispersion, and live cell imaging showed that cluster dispersion involved initial fragmentation of tight clusters into multiple smaller clusters, which then fragmented into well-dispersed individual CLD. siRNA knockdown of the cortical actin binding protein, moesin, induced disaggregation of tight clusters into multiple smaller clusters, and inhibited the reaggregation of dispersed CLD into tight clusters. Together these data suggest that the clustering and dispersion processes involve a complex orchestration of phosphorylation-dependent, microtubule-dependent and independent, and microfilament dependent steps. PMID:23825572

  2. Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics

    Science.gov (United States)

    Lau, Gabriel V.; Hunt, Patricia A.; Müller, Erich A.; Jackson, George; Ford, Ian J.

    2015-12-01

    Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the "mitosis" or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study.

  3. Determining dynamic parameters of different-scale ionospheric irregularities over northern Siberia

    Science.gov (United States)

    Afraimovich, E. L.; Lipko, Y. V. Y. V.; Vugmeister, B. O.

    2000-01-01

    In 1995-1996, observations were carried out at Norilsk (geomagnetic latitude and longitude 64.2 degN and 160.4 degE) to determine dynamic parameters of irregularities in the high-latitude ionosphere. The short-baseline spaced-receiver method that has been implemented at the ionospheric facility of the Norilsk Integrated Magnetic-Ionospheric Station, provides a means of simultaneously measuring parameters of small-scale irregularities (spatial scale of 3-5 km) by the Similar-Fading Method (SFM), as well as of medium-scale irregularities (time scale of 10-30 min, spatial scale of hundreds of kilometres) by the Statistical Angle-of-arrival and Doppler Method (SADM). About 20 h of the observational data for the F2-layer under quiet geomagnetic conditions (Kp = 3) and about 15 h for the sporadic E-layer (Kp ~ 3) were processed. It has been found that the propagation directions and velocities of different-scale irregularities do not coincide. Small-scale irregularities of the F2-layer travel predominantly eastward or westward. The velocity of the F2-layer irregularities is about 100 m/s, and under disturbed conditions it is up to 200-250 m/s. Small-scale irregularities of the sporadic E-layer travel mostly in the northward direction. It is confirmed that the Es-layer is characterised by high velocities of the irregularities (as high as 1000 m/s). Medium-scale irregularities with periods in the range of 10-30 min travel mostly in a southward direction with velocities of 20-40 m/s.

  4. Climate warming and agricultural stressors interact to determine stream macroinvertebrate community dynamics.

    Science.gov (United States)

    Piggott, Jeremy J; Townsend, Colin R; Matthaei, Christoph D

    2015-05-01

    Global climate change is likely to modify the ecological consequences of currently acting stressors, but potentially important interactions between climate warming and land-use related stressors remain largely unknown. Agriculture affects streams and rivers worldwide, including via nutrient enrichment and increased fine sediment input. We manipulated nutrients (simulating agricultural run-off) and deposited fine sediment (simulating agricultural erosion) (two levels each) and water temperature (eight levels, 0-6°C above ambient) simultaneously in 128 streamside mesocosms to determine the individual and combined effects of the three stressors on macroinvertebrate community dynamics (community composition and body size structure of benthic, drift and insect emergence assemblages). All three stressors had pervasive individual effects, but in combination often produced additive or antagonistic outcomes. Changes in benthic community composition showed a complex interplay among habitat quality (with or without sediment), resource availability (with or without nutrient enrichment) and the behavioural/physiological tendency to drift or emerge as temperature rose. The presence of sediment and raised temperature both resulted in a community of smaller organisms. Deposited fine sediment strongly increased the propensity to drift. Stressor effects were most prominent in the benthic assemblage, frequently reflected by opposite patterns in individuals quitting the benthos (in terms of their propensity to drift or emerge). Of particular importance is that community measures of stream health routinely used around the world (taxon richness, EPT richness and diversity) all showed complex three-way interactions, with either a consistently stronger temperature response or a reversal of its direction when one or both agricultural stressors were also in operation. The negative effects of added fine sediment, which were often stronger at raised temperatures, suggest that streams already

  5. Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Lau, Gabriel V.; Müller, Erich A.; Jackson, George [Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Hunt, Patricia A. [Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Ford, Ian J. [Department of Physics and Astronomy and London Centre for Nanotechnology, University College London, Gower Street, London WC1E 6BT (United Kingdom)

    2015-12-28

    Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the “mitosis” or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study.

  6. Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics.

    Science.gov (United States)

    Lau, Gabriel V; Hunt, Patricia A; Müller, Erich A; Jackson, George; Ford, Ian J

    2015-12-28

    Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the "mitosis" or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study.

  7. Hydrogen dynamics in soil organic matter as determined by 13C and 2H labeling experiments

    Science.gov (United States)

    Paul, Alexia; Hatté, Christine; Pastor, Lucie; Thiry, Yves; Siclet, Françoise; Balesdent, Jérôme

    2016-12-01

    Understanding hydrogen dynamics in soil organic matter is important to predict the fate of 3H in terrestrial environments. One way to determine hydrogen fate and to point out processes is to examine the isotopic signature of the element in soil. However, the non-exchangeable hydrogen isotopic signal in soil is complex and depends on the fate of organic compounds and microbial biosyntheses that incorporate water-derived hydrogen. To decipher this complex system and to understand the close link between hydrogen and carbon cycles, we followed labeled hydrogen and labeled carbon throughout near-natural soil incubations. We performed incubation experiments with three labeling conditions: 1 - 13C2H double-labeled molecules in the presence of 1H2O; 2 - 13C-labeled molecules in the presence of 2H2O; 3 - no molecule addition in the presence of 2H2O. The preservation of substrate-derived hydrogen after 1 year of incubation (ca. 5 % in most cases) was lower than the preservation of substrate-derived carbon (30 % in average). We highlighted that 70 % of the C-H bonds are broken during the degradation of the molecule, which permits the exchange with water hydrogen. Added molecules are used more for trophic resources. The isotopic composition of the non-exchangeable hydrogen was mainly driven by the incorporation of water hydrogen during microbial biosynthesis. It is linearly correlated with the amount of carbon that is degraded in the soil. The quantitative incorporation of water hydrogen in bulk material and lipids demonstrates that non-exchangeable hydrogen exists in both organic and mineral-bound forms. The proportion of the latter depends on soil type and minerals. This experiment quantified the processes affecting the isotopic composition of non-exchangeable hydrogen, and the results can be used to predict the fate of tritium in the ecosystem or the water deuterium signature in organic matter.

  8. Dynamic karyotype evolution and unique sex determination systems in Leptidea wood white butterflies.

    Science.gov (United States)

    Šíchová, Jindra; Voleníková, Anna; Dincă, Vlad; Nguyen, Petr; Vila, Roger; Sahara, Ken; Marec, František

    2015-05-19

    Chromosomal rearrangements have the potential to limit the rate and pattern of gene flow within and between species and thus play a direct role in promoting and maintaining speciation. Wood white butterflies of the genus Leptidea are excellent models to study the role of chromosome rearrangements in speciation because they show karyotype variability not only among but also within species. In this work, we investigated genome architecture of three cryptic Leptidea species (L. juvernica, L. sinapis and L. reali) by standard and molecular cytogenetic techniques in order to reveal causes of the karyotype variability. Chromosome numbers ranged from 2n = 85 to 91 in L. juvernica and 2n = 69 to 73 in L. sinapis (both from Czech populations) to 2n = 51 to 55 in L. reali (Spanish population). We observed significant differences in chromosome numbers and localization of cytogenetic markers (rDNA and H3 histone genes) within the offspring of individual females. Using FISH with the (TTAGG) n telomeric probe we also documented the presence of multiple chromosome fusions and/or fissions and other complex rearrangements. Thus, the intraspecific karyotype variability is likely due to irregular chromosome segregation of multivalent meiotic configurations. The analysis of female meiotic chromosomes by GISH and CGH revealed multiple sex chromosomes: W1W2W3Z1Z2Z3Z4 in L. juvernica, W1W2W3Z1Z2Z3 in L. sinapis and W1W2W3W4Z1Z2Z3Z4 in L. reali. Our results suggest a dynamic karyotype evolution and point to the role of chromosomal rearrangements in the speciation of Leptidea butterflies. Moreover, our study revealed a curious sex determination system with 3-4 W and 3-4 Z chromosomes, which is unique in the Lepidoptera and which could also have played a role in the speciation process of the three Leptidea species.

  9. QM/MM-MD simulations of conjugated polyelectrolytes

    DEFF Research Database (Denmark)

    Sjöqvist, Jonas; Linares, Mathieu; Mikkelsen, Kurt Valentin

    2014-01-01

    description of the solvent in its electronic ground state as well as the chromophore in its electronic ground and excited states, (ii) a conformational sampling by means of classical molecular dynamics (MD) in the respective electronic states, and (iii) spectral response calculations by means of the quantum...

  10. Climate determined differences in carbon dioxide fluxes dynamics between two comparable agroecosystems of Central Russia

    Science.gov (United States)

    Yaroslavtsev, Alexis; Meshalkina, Joulia; Mazirov, Ilya; Valentini, Riccardo; Vasenev, Ivan

    2015-04-01

    fields. Pristen field's soil water content was higher through the growing season due to better chernozem's moisture retention capacity. Amount and dynamics of precipitation and as a result soil water content at studied plots differed distinctly. Moscow field had a higher precipitation values. Diurnal values of net ecosystem exchange (NEE) clearly showed significant interseasonal and interplot differences. Diurnal patterns of NEE were considerably higher in Pristen site with similar to Moscow patterns for all months of growing season, except May due to earlier sowing in Chernozem region. Maximal CO2 sink were observed during June for both fields and made -6 and -3 g C CO2 m-2 d-1, for Pristen and Moscow fields, respectively. The Pristen site showed similar sink values and dynamics for May. Main GPP dynamics driver was different crop development stage: Pristen's barley earlier sowing and longer growing period. Higher GPP values were due to better climate and soil parameters in Pristen (higher PAR, temperature and soil moisture). The number of net sink days for Pristen and Moscow fields were 85 and 67 days, respectively. All cumulative functions for growing season were consistently higher in Pristen than in Moscow: cumulative NEE were -160 g C CO2 m-2 and -80 g C CO2 m-2, cumulative Reco were 450 g CCO2 m-2 and 300 g C CO2 m-2, cumulative GPP were 610 g C CO2 m-2 and 380 g C CO2 m-2, respectively. As a result, we can conclude that essentially higher GPP values were in Pristen due to its better climate and soil parameters (higher PAR, temperature and soil moisture). General trends for ecosystem's respiration (Reco) and GPP were determined by crop phase. Reco peaks corresponded well to raining periods. Differences in carbon loss can be explained by differences in soil microbial community due to different soil type, what highlights important role of soil in carbon exchange for agroecosystems. Obtained unique for Russian agriculture data will be used for land-use models

  11. ANALYSIS OF METHOD FOR DETERMINING AZIMUTH OF PRINCIPAL AXIS OF INERTIA BASED ON DYNAMIC BALANCE MEASUREMENT

    Institute of Scientific and Technical Information of China (English)

    ZHAO Jun; GUAN Yingzi; QI Naiming

    2006-01-01

    The dynamic balance quality of a rotating object is an important factor to maintain the stability and accuracy for motion. The azimuth of the principal axis of inertia is a major sign of dynamic balance. A usual method is measuring moment of inertia matrix relative to some base coordinates on a rotary inertia machine so as to calculate the azimuth of principal axis of inertia. By using the measured unbalance results on the two trimmed planes on a vertical hard bearing double-plane dynamic balancing machine, the dimension and direction of couple unbalance can be found. An azimuth angle formula for the principal axis of inertia is derived and is solved by using unbalance quantities. The experiments indicate that method based on dynamic balancing measurement is proved rational and effective and has a fine precision.

  12. Determining the Role of Dynamic Hyperinflation in Patients with Severe Chronic Obstructive Pulmonary Disease

    NARCIS (Netherlands)

    Klooster, Karin; ten Hacken, Nick H. T.; Hartman, Jorine E.; Sciurba, Frank C.; Kerstjens, Huib A. M.; Slebos, Dirk-Jan

    2015-01-01

    Background: Dynamic hyperinflation due to increased respiratory frequency during exercise is associated with limitations in exercise capacity in patients with moderately severe chronic obstructive pulmonary disease (COPD). Objectives: The present study assessed whether the manually paced tachypnea (

  13. Determination of bimetallic architectures in nanometer-scale catalysts by combining molecular dynamics simulations with x-ray absorption spectroscopy

    Science.gov (United States)

    Timoshenko, Janis; Keller, Kayla R.; Frenkel, Anatoly I.

    2017-03-01

    Here we present an approach for the determination of an atomic structure of small bimetallic nanoparticles by combining extended X-ray absorption fine structure spectroscopy and classical molecular dynamics simulations based on the Sutton-Chen potential. The proposed approach is illustrated in the example of PdAu nanoparticles with ca 100 atoms and narrow size and compositional distributions. Using a direct modeling approach and no adjustable parameters, we were able to reproduce the size and shape of nanoparticles as well as the intra-particle distributions of atoms and metal mixing ratios and to explore the influence of these parameters on the local structure and dynamics in nanoparticles.

  14. DYNAMICS AND THEIR DETERMINANTS IN HOUSEHOLD DEPOSITS IN LEI. CASE OF ROMANIA AFTER THE FINANCIAL CRISIS OF 2008

    Directory of Open Access Journals (Sweden)

    Zaharia Marian

    2015-12-01

    Full Text Available In the article are examined on the one hand the dynamics of household deposits as the important component of saving behaviour and on the other hand the most important determinants of household deposits behaviour. The paper was structured in 4 sections. The first section represents a short overview of the related literature. Source data and methodological aspects are described in section 2. The dynamics of the population's deposits, is discussed in section 3, while section 4 explains the results obtained from the analysis carried out. The results of this study confirm the direct and influence of the variable like the exchange rate on the household deposits.

  15. 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.

  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. Environmental factors that determine the occurrence and seasonal dynamics of Aphanizomenon flos-aquae

    Directory of Open Access Journals (Sweden)

    Yoshimasa YAMAMOTO

    2009-02-01

    Full Text Available This study investigated the seasonal dynamics of two populations of Aphanizomenon flos-aquae Ralfs ex Bornet & Flahault var. flos-aquae and four populations of A. flos-aquae var. klebahnii Elenkin in eutrophic water bodies over 1 year from February 2006 to January 2007. The growth of A. flos-aquae var. flos-aquae was promoted at high temperatures even if in one case the biomass development was very low when other co-occurring cyanoprokaryotes (Anabaena spp. and Microcystis spp. were abundant. In contrast, the highest density of the other population of A. flos-aquae var. flos-aquae was observed in August when the population density of M. aeruginosa (Kützing Kützing reached an annual peak. A. flos-aquae var. flos-aquae usually bloomed in summer but could also tolerate low temperatures in the winter, and was present in relatively high densities. The populations of A. flos-aquae var. klebahnii observed in this study can be divided into three groups based on preferred temperature; three populations increased in winter, and the other increased in summer. Large biomasses of the low-temperature-adapted A. flos-aquae were observed mainly during winter when population densities of co-occurring cyanoprokaryotes (Anabaena spp., Microcystis spp. and Planktothrix raciborskii (Woloszynska Anagnostidis & Komárek were relatively low or almost absent. The increase in or existence of cooccurring cyanoprokaryotes during the summer resulted in a decrease of the A. flos-aquae population density. It was revealed that high temperatures (20-25 °C are suitable for maintaining A. flos-aquae var. klebahnii strains isolated from the study ponds, implying that low-temperature-adapted A. flos-aquae can grow over a wide range of water temperatures. The high-temperatureadapted A. flos-aquae var. klebahnii co-existed with M. aeruginosa during summer; however, its peak population density was significantly lower than those in previous years when M. aeruginosa was absent

  18. Impact of static and dynamic A-form heterogeneity on the determination of RNA global structural dynamics using NMR residual dipolar couplings

    Energy Technology Data Exchange (ETDEWEB)

    Musselman, Catherine [University of Michigan, Department of Chemistry, Biophysics Research Division, and Program in Bioinformatics (United States); Pitt, Stephen W. [Johnson and Johnson Inc (United States); Gulati, Kush; Foster, Lesley L.; Andricioaei, Ioan; Al-Hashimi, Hashim M. [University of Michigan, Department of Chemistry, Biophysics Research Division, and Program in Bioinformatics (United States)], E-mail: hashimi@umich.edu

    2006-12-15

    We examined how static and dynamic deviations from the idealized A-form helix propagate into errors in the principal order tensor parameters determined using residual dipolar couplings (rdcs). A 20-ns molecular dynamics (MD) simulation of the HIV-1 transactivation response element (TAR) RNA together with a survey of spin relaxation studies of RNA dynamics reveals that pico-to-nanosecond local motions in non-terminal Watson-Crick base-pairs will uniformly attenuate base and sugar one bond rdcs by {approx}7%. Gaussian distributions were generated for base and sugar torsion angles through statistical comparison of 40 RNA X-ray structures solved to <3.0 A resolution. For a typical number ({>=}11) of one bond C-H base and sugar rdcs, these structural deviations together with rdc uncertainty (1.5 Hz) lead to average errors in the magnitude and orientation of the principal axis of order that are <9% and <4 deg., respectively. The errors decrease to <5% and <4 deg. for {>=}17 rdcs. A protocol that allows for estimation of error in A-form order tensors due to both angular deviations and rdc uncertainty (Aform-RDC) is validated using theoretical simulations and used to analyze rdcs measured previously in TAR in the free state and bound to four distinct ligands. Results confirm earlier findings that the two TAR helices undergo large changes in both their mean relative orientation and dynamics upon binding to different targets.

  19. Investigating On-Orbit Attitude Determination Anomalies for the Solar Dynamics Observatory Mission

    Science.gov (United States)

    Vess, Melissa F.; Starin, Scott R.; Chia-Kuo, Alice Liu

    2011-01-01

    The Solar Dynamics Observatory (SDO) was launched on February 11, 2010 from Kennedy Space Center on an Atlas V launch vehicle into a geosynchronous transfer orbit. SDO carries a suite of three scientific instruments, whose observations are intended to promote a more complete understanding of the Sun and its effects on the Earth's environment. After a successful launch, separation, and initial Sun acquisition, the launch and flight operations teams dove into a commissioning campaign that included, among other things, checkout and calibration of the fine attitude sensors and checkout of the Kalman filter (KF) and the spacecraft s inertial pointing and science control modes. In addition, initial calibration of the science instruments was also accomplished. During that process of KF and controller checkout, several interesting observations were noticed and investigated. The SDO fine attitude sensors consist of one Adcole Digital Sun Sensor (DSS), two Galileo Avionica (GA) quaternion-output Star Trackers (STs), and three Kearfott Two-Axis Rate Assemblies (hereafter called inertial reference units, or IRUs). Initial checkout of the fine attitude sensors indicated that all sensors appeared to be functioning properly. Initial calibration maneuvers were planned and executed to update scale factors, drift rate biases, and alignments of the IRUs. After updating the IRU parameters, the KF was initialized and quickly reached convergence. Over the next few hours, it became apparent that there was an oscillation in the sensor residuals and the KF estimation of the IRU bias. A concentrated investigation ensued to determine the cause of the oscillations, their effect on mission requirements, and how to mitigate them. The ensuing analysis determined that the oscillations seen were, in fact, due to an oscillation in the IRU biases. The low frequencies of the oscillations passed through the KF, were well within the controller bandwidth, and therefore the spacecraft was actually

  20. 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}.